Antimicrobial solutions and process related thereto

ABSTRACT

Disclosed are antimicrobial compositions for treating poultry, meat, and other surfaces to substantially eliminate bacteria and microorganism harmful to humans. The compositions include a combination of an aliphatic heteroaryl salt, trichloromelamine, and at least two ammonium salts comprising an aliphatic benzylalkyl ammonium salt, dialiphatic dialkyl ammonium salt, or a tetraalkyl ammonium salt.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of International ApplicationNo. PCT/US2004/006599, filed Mar. 5, 2004. Application PCT/US2004/006599claims benefit of priority to U.S. Provisional Application No.60/451,678, filed Mar. 5, 2003, and U.S. Provisional Application No.60/507,949 filed Oct. 3, 2003. International Application No.PCT/US2004/006599 and U.S. Provisional Application Nos. 60/451,678 and60/507,949 are each incorporated by reference herein in theirentireties.

FIELD

The disclosed matter generally relates to compositions and methods forreducing or preventing microorganism growth or survival. Morespecifically, the disclosed matter relates to compositions and methodsfor treating meat and poultry to eliminate pathogenic microorganisms.

BACKGROUND

Prevention of food-borne illness has been of paramount concern for thefood industry, the public, and the regulatory agencies. The Centers forDisease Control and Prevention (CDC) conducted an evaluation to betterquantify the impact of food-borne diseases on health in the U.S. (Mead,et al., Food-Related Illness and Death in the United States, Centers forDisease Control and Prevention, Atlanta, Ga., USA, 2003). The reportestimated that food-borne diseases cause approximately 76 millionillnesses, 325,000 hospitalizations, and 5,000 deaths in the U.S. eachyear. Known pathogens account for an estimated 14 million illnesses,60,000 hospitalizations, and 1,800 deaths. Three pathogens, Salmonella,Listeria, and Toxoplasma, are responsible for 1,500 deaths each year,more than 75% of those deaths caused by known pathogens, while unknownagents account for the remaining 62 million illnesses, 265,000hospitalizations, and 3,200 deaths. Other food-borne microorganisms thatare of public health concern include Aeromonas hydrophila, Arcobacterbutzleri, Bacillus cereus, Campylobacter jejuni, Escherichia coli, andStaphylococcus aureus. Fred R. Shank, Director of the Center for FoodSafety and Applied Nutrition of the Food and Drug Administrationtestified before the U.S. Congress that the yearly cost of food-borneillness in the U.S. is between $7.7 and $23 billion.

Salmonella is one of the more common intestinal infections withpotentially fatal consequences. The CDC reports that every yearapproximately 40,000 cases of salmonellosis are reported in the U.S.Because many milder cases are not diagnosed or reported, the actualnumber of infections is likely much higher. Salmonellosis is more commonin warmer months than during the winter months. And the most likely tohave severe infections are young children, the elderly, and theimmuno-compromised. It is estimated that approximately 600 persons dieeach year with acute salmonellosis.

Salmonella and many other microorganisms can adhere to poultry, meat,and other food tissues, making removal of the microorganisms difficultwith rinsing alone. Consequently, treatments including irradiation,chemical treatment, and physical processing have been used to addressthe problem of microorganism contamination of food. For example,trisodium phosphate has been used in poultry processing to eliminateSalmonella typhimurium. However, studies have provided conflictingresults on efficacy of trisodium phosphate against treating Salmonella.

A common problem with many treatments is that they may be effectiveagainst one type of microorganism but not others. For example, U.S. Pat.No. 5,366,983 discloses a composition containing an aqueous solution ofa quaternary ammonium compound (“QAC”). It has been reported, however,that QAC's including alkyl pyridinium halides (such as cetylpyridiniumchloride (“CPC”) and cetylpyridinium bromide (“CPB”)) were effective inremoving Salmonella but not other types of microorganisms. It has alsobeen found that treatment with CPC requires contacting the meat orpoultry with large quantities of CPC for long periods of time. Thisrequires costly downstream processing steps to remove the CPC.Typically, this is done by recapturing the product as it is sprayed andhauled out, similar to toxic waste.

U.S. Pat. No. 5,855,940 also discloses a composition containing a QACfor inhibiting attachment of and removing pathogenic toxin-producingEscherichia contamination. This patent discloses a compositioncontaining QAC selected from the group consisting of alkyl pyridinium,tetraalkylammonium, and alkylalicyclic ammonium salts in an aqueoussolution.

Other treatment methods include treatment with a chlorine solution orwith a solution of tri-sodium phosphate. Chlorine solutions have beenfound ineffective in eliminating all of the pathogenic microorganisms.Also, when chlorine is added to a solution or water, the efficacy of thechloride is only as good as the mole concentration of the chloride ion.The concentration of chloride ion can decrease rapidly due to the ioninteracting with, for example, nascent oxygen. Tri-sodium phosphate hasbeen used during the reprocessing stage where the inside and outside ofthe poultry is sanitized. This process, however, requires filtering thereprocessor's water before disposal in order to remove tri-sodiumphosphate. Still other common antimicrobial compositions that are used,while effective on some surfaces, can not be used on food surfaces dueto their toxicity.

Presently, there are no known effective antimicrobial compositions thatare effective against a broad range of microorganisms and can be safelybe used on food surfaces. Accordingly, there is a need for antimicrobialcompositions and methods for treating contaminated food such as poultryand meat to eliminate a broad range of microorganisms. Further there isalso a need for antimicrobial compositions that can be effectively beused on other surfaces, such as floors, coolers, tables, trays, and thelike. The antimicrobial compositions and methods disclosed herein meetthese and other needs.

SUMMARY

In accordance with the purposes of the disclosed materials, compounds,compositions, and methods, as embodied and broadly described herein, thedisclosed matter, in one aspect, relates to compositions and methods forpreparing and using such compositions. In another aspect, disclosedherein are antimicrobial compositions and methods for using suchcompositions to reduce, prevent, or eliminate a microorganism, such as afood-borne microorganism on poultry and meat.

The advantages described below will be realized and attained by means ofthe elements and combinations particularly pointed out in the appendedclaims. It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are not restrictive.

BRIEF DESCRIPTION OF THE FIGURES

The accompanying figures, which are incorporated in and constitute apart of this specification, illustrate several aspects described below.

FIG. 1 is a flow chart showing the steps taken in poultry processing.

FIG. 2 is a flow chart showing a poultry processing method according toone aspect of the disclosed subject matter.

In the following figures “ST” refers to Salmonella typhimurium, “LM”refers to Listeria monocytogenes, “SA” refers to Staphylococcus aureau,“EC” refers to Escherichia coli, “PF” refers to Pseudomonas fluorscens,and “SP” refers to Shewanella putrefaciens. Also, an antimicrobialcomposition as disclosed herein is indicated as “Test Solution” and acontrol solution is indicated as “Controls.”

FIG. 3 is a graph showing the effect of an antimicrobial composition asdisclosed herein and a control solution on pathogenic and spoilagebacterial isolates. The results are shown in terms of detection times(hours). Detection times of 24 hours mean no growth occurred afterexposure to test solution.

FIG. 4 is a graph showing the reduction of the indicated bacterialcolonies (in log₁₀ colony forming units) when exposed to anantimicrobial composition as disclosed herein or a control solution.

FIG. 5 is a graph showing the effect of an antimicrobial composition asdisclosed herein and control solution on the indicated bacterialisolates. The results are shown in terms of detection times (hours).Detection times of 24 hours mean no growth occurred after exposure totest solution.

FIG. 6 is a graph showing the reduction of indicated bacterial colonies(in log₁₀ colony forming units) when exposed to an antimicrobialcomposition as disclosed herein or a control solution.

FIG. 7 is a graph showing the effect of an antimicrobial composition asdisclosed herein and a control solution when used to treat the indicatedmicroorganisms attached to food contact surfaces. The results are shownin terms of detection times (hours). Detection times of 24 hours mean nogrowth occurred after exposure to test solution.

FIG. 8 is a graph comparing Salmonella content (in log₁₀ colony formingunits) in control samples treated with water and samples treated with adiluted antimicrobial composition as disclosed herein.

FIG. 9 is a graph comparing E. coli or coliforms microbial content (inlog₁₀ colony forming units) in control samples treated with water andsamples treated with a diluted antimicrobial composition as disclosedherein.

DETAILED DESCRIPTION

The materials, compositions, articles, devices, and methods describedherein may be understood more readily by reference to the followingdetailed description of specific aspects of the disclosed subjectmatter, and methods and the Examples included therein and to the Figuresand their previous and following description.

Before the present materials, compositions, articles, devices, andmethods are disclosed and described, it is to be understood that theaspects described below are not limited to specific synthetic methods orspecific reagents, as such may, of course, vary. It is also to beunderstood that the terminology used herein is for the purpose ofdescribing particular aspects only and is not intended to be limiting.

Also, throughout this specification, various publications arereferenced. The disclosures of these publications in their entiretiesare hereby incorporated by reference into this application in order tomore fully describe the state of the art to which the disclosed subjectmatter pertains. The references disclosed are also individually andspecifically incorporated by reference herein for the material containedin them that is discussed in the sentence in which the reference isrelied upon.

General Definitions

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “a compound”includes mixtures of two or more such compounds, reference to “an agent”includes mixtures of two or more such agents, reference to “thecomposition” includes mixtures of two or more such compositions, and thelike.

Throughout the specification and claims, the word “comprise” andvariations of the word, such as “comprising” and “comprises,” means“including but not limited to,” and is not intended to exclude, forexample, other additives, components, integers, or steps.

“Optional” or “optionally” means that the subsequently described eventor circumstance can or cannot occur, and that the description includesinstances where the event or circumstance occurs and instances where itdoes not.

Ranges can be expressed herein as from “about” one particular value,and/or to “about” another particular value. When such a range isexpressed, another embodiment includes from the one particular valueand/or to the other particular value. Similarly, when values areexpressed as approximations, by use of the antecedent “about,” it willbe understood that the particular value forms another embodiment. Itwill be further understood that the endpoints of each of the ranges aresignificant both in relation to the other endpoint, and independently ofthe other endpoint. It is also understood that there are a number ofvalues disclosed herein, and that each value is also herein disclosed as“about” that particular value in addition to the value itself. Forexample, if the value “10” is disclosed, then “about 10” is alsodisclosed. It is also understood that when a value is disclosed that“less than or equal to” the value, “greater than or equal to the value”and possible ranges between values are also disclosed, as appropriatelyunderstood by the skilled artisan. For example, if the value “10” isdisclosed then “less than or equal to 10” as well as “greater than orequal to 10” is also disclosed. It is also understood that thethroughout the application, data is provided in a number of differentformats, and that this data, represents endpoints and starting points,and ranges for any combination of the data points. For example, if aparticular data point “10” and a particular data point “15” aredisclosed, it is understood that greater than, greater than or equal to,less than, less than or equal to, and equal to 10 and 15 are considereddisclosed as well as between 10 and 15. It is also understood that eachunit between two particular units are also disclosed. For example, if 10and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

References in the specification and claims to parts by weight of aparticular element or component in a composition or article denotes theweight relationship between the element or component and any otherelements or components in the composition or article for which a part byweight is expressed. Thus, in a compound containing 2 parts by weight ofcomponent X and 5 parts by weight component Y, X and Y are present at aweight ratio of 2:5, and are present in such ratio regardless of whetheradditional components are contained in the compound.

A weight percent of a component, unless specifically stated to thecontrary, is based on the total weight of the formulation or compositionin which the component is included.

By “reduce” or other forms of the word, such as “reducing” or“reduction,” is meant lowering of an event or characteristic (e.g.,microorganism growth or survival). It is understood that this istypically in relation to some standard or expected value, in other wordsit is relative, but that it is not always necessary for the standard orrelative value to be referred to. For example, “reduces the populationof bacteria” means lowering the amount of bacteria relative to astandard or a control.

By “prevent” or other forms of the word, such as “preventing” or“prevention,” is meant to stop a particular event or characteristic, tostabilize or delay the development or progression of a particular eventor characteristic, or to minimize the chances that a particular event orcharacteristic will occur. Prevent does not require comparison to acontrol as it is typically more absolute than, for example, reduce. Asused herein, something could be reduced but not prevented, but somethingthat is reduced could also be prevented. Likewise, something could beprevented but not reduced, but something that is prevented could also bereduced. It is understood that where reduce or prevent are used, unlessspecifically indicated otherwise, the use of the other word is alsoexpressly disclosed.

By “treat” or other forms of the word, such as “treated” or “treatment,”is meant to administer a composition or to perform a method in order toreduce, prevent, inhibit, break-down, or eliminate a particularcharacteristic or event (e.g., microorganism growth or survival).

By “antimicrobial” is meant the ability to treat (e.g., reduce, prevent,inhibit, break-down, or eliminate) microorganism growth or survival atany concentration.

Chemical Definitions

As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, and aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,for example, those described below. The permissible substituents can beone or more and the same or different for appropriate organic compounds.For purposes of this disclosure, the heteroatoms, such as nitrogen andoxygen, can have hydrogen substituents and/or any permissiblesubstituents of organic compounds described herein which satisfy thevalencies of the heteroatoms. This disclosure is not intended to belimited in any manner by the permissible substituents of organiccompounds. Also, the terms “substitution” or “substituted with” includethe implicit proviso that such substitution is in accordance withpermitted valence of the substituted atom and the substituent, and thatthe substitution results in a stable compound, e.g., a compound thatdoes not spontaneously undergo transformation such as by rearrangement,cyclization, elimination, etc. Also, as used herein “substitution” or“substituted with” is meant to encompass configurations where onesubstituent is fused to another substituent. For example, an alkyl groupsubstituted with an aryl group (or vice versa) can mean that the arylgroup is bonded to the alkyl group via a single sigma bond and also thatthe aryl group and alkyl group are fused, e.g., two carbons of the alkylgroup are shared with two carbons of the aryl group.

“A¹,” “A²,” “A³,” and “A⁴” are used herein as generic symbols torepresent various specific substituents. These symbols can be anysubstituent, not limited to those disclosed herein, and when they aredefined to be certain substituents in one sentence it does not meanthat, in another sentence, they cannot be defined as some othersubstituents.

The term “alkyl” as used herein is a branched or unbranched saturatedhydrocarbon group of 1 to 40 carbon atoms, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl,tetracosyl, and the like. The alkyl group can also be substituted orunsubstituted. The alkyl group can be substituted with one or moregroups including, but not limited to, alkyl, halogenated alkyl, alkoxy,alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid,ester, ether, halide, hydroxy, ketone, sulfo-oxo, sulfonylamino, nitro,silyl, or thiol, as described below.

Throughout the specification “alkyl” is generally used to refer to bothunsubstituted alkyl groups and substituted alkyl groups; however,substituted alkyl groups are also specifically referred to herein byidentifying the specific substituent(s) on the alkyl group. For example,the term “alkyl halide” specifically refers to an alkyl group that issubstituted with one or more halides, e.g., fluorine, chlorine, bromine,or iodine. When “alkyl” is used in one sentence and a specific term suchas “alkyl halide” is used in another, it is not meant to imply that theterm “alkyl” does not also refer to specific terms such as “alkylhalide” and the like.

This practice is also used for other groups described herein. That is,while a term such as “heteroaryl” refers to both unsubstituted andsubstituted heteroaryl moieties, the substituted moieties can, inaddition, be specifically identified herein; for example, a particularsubstituted heteroaryl can be referred to as, e.g., an “alkylheteroaryl.” Similarly, a substituted alkenyl can be, e.g., an “alkenylhalide,” and the like. Again, the practice of using a general term, suchas “heteroaryl,” and a specific term, such as “alkyl heteroaryl,” is notmeant to imply that the general term does not also include the specificterm.

The term “alkenyl” as used herein is a hydrocarbon group of from 2 to 40carbon atoms with a structural formula containing at least onecarbon-carbon double bond. Asymmetric structures such as (A¹A²)C═C(A³A⁴)are intended to include both the E and Z isomers. This may be presumedin structural formulae herein wherein an asymmetric alkene is present,or it may be explicitly indicated by the bond symbol C═C. The alkenylgroup can be substituted with one or more groups including, but notlimited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl,heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,hydroxy, ketone, sulfo-oxo, sulfonylamino, nitro, silyl, or thiol.

The term “alkynyl” as used herein is a hydrocarbon group of 2 to 40carbon atoms with a structural formula containing at least onecarbon-carbon triple bond. The alkynyl group can be substituted with oneor more groups including, but not limited to, alkyl, halogenated alkyl,alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylicacid, ester, ether, halide, hydroxy, ketone, sulfo-oxo, sulfonylamino,nitro, silyl, or thiol.

The term “aliphatic” as used herein refers to a non-aromatic hydrocarbongroup and includes branched and unbranched, alkyl, alkenyl, or alkynylgroups.

The term “aryl” as used herein is a group that contains any carbon-basedaromatic group including, but not limited to, benzene, benzyl,naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term“aryl” also includes “heteroaryl,” which is defined as a group thatcontains an aromatic group that has at least one heteroatom incorporatedwithin the ring of the aromatic group. Examples of heteroatoms include,but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.Likewise, the term “non-heteroaryl,” which is also included in the term“aryl,” defines a group that contains an aromatic group that does notcontain a heteroatom. The aryl group can be substituted orunsubstituted. The aryl group can be substituted with one or more groupsincluding, but not limited to, alkyl, halogenated alkyl, alkoxy,alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid,ester, ether, halide, hydroxy, ketone, sulfo-oxo, sulfonylamino, orthiol as described herein. The term “biaryl” is a specific type of arylgroup and is included in the definition of aryl. Biaryl refers to twoaryl groups that are bound together via a fused ring structure, as innaphthalene, or are attached via one or more carbon-carbon bonds, as inbiphenyl.

The term “cycloalkyl” as used herein is a non-aromatic carbon-based ringcomposed of at least three carbon atoms. Examples of cycloalkyl groupsinclude, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, etc. The term “heterocycloalkyl” is a cycloalkyl group asdefined above where at least one of the carbon atoms of the ring issubstituted with a heteroatom such as, but not limited to, nitrogen,oxygen, sulfur, or phosphorus. The cycloalkyl group and heterocycloalkylgroup can be substituted or unsubstituted. The cycloalkyl group andheterocycloalkyl group can be substituted with one or more groupsincluding, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl,heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,hydroxy, ketone, sulfo-oxo, sulfonylamino, nitro, silyl, or thiol.

The term “cycloalkenyl” as used herein is a non-aromatic carbon-basedring composed of at least three carbon atoms and contains at least onedouble bound, e.g., C═C. Examples of cycloalkenyl groups include, butare not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl,cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like. The term“heterocycloalkenyl” is a type of cycloalkenyl group as defined above,and is included within the meaning of the term “cycloalkenyl,” where atleast one of the carbon atoms of the ring is substituted with aheteroatom such as, but not limited to, nitrogen, oxygen, sulfur, orphosphorus. The cycloalkenyl group and heterocycloalkenyl group can besubstituted or unsubstituted. The cycloalkenyl group andheterocycloalkenyl group can be substituted with one or more groupsincluding, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl,heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,hydroxy, ketone, sulfo-oxo, sulfonylamino, nitro, silyl, or thiol.

The term “cyclic group” is used herein to refer to either aryl groups(e.g., heteraryl, biaryl), non-aryl groups (i.e., cycloalkyl,heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl groups), or both.Cyclic groups have one or more ring systems that can be substituted orunsubstituted. A cyclic group can contain one or more aryl groups, oneor more non-aryl groups, or one or more aryl groups and one or morenon-aryl groups.

The terms “amine” or “amino” as used herein are represented by theformula:

where A¹, A², and A³ can each be, independent of one another, hydrogen,an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl,cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl groupdescribed above. Also, any of the A¹, A², and A³ substituents can beabsent and any of the remaining substituents can be a multivalent group,i.e., form more than one bond with N.

The terms “ammonium” or “quaternary ammonium” are represented by theformula:

where A¹, A², A³, and A⁴ can each be, independent of one another,hydrogen, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl,heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, orheterocycloalkenyl group described above. Also, any of the A¹, A², A³,and A⁴ substituents can be absent and any of the remaining substituentscan be a multivalent group.

The term “halide” as used herein refers to the halogens fluorine,chlorine, bromine, and iodine.

“X,” “R¹,” “R²,” and “R^(n),” where n is some integer, as used hereincan, independently, possess two or more of the groups listed above. Forexample, if R is a straight chain alkyl group, one of the hydrogen atomsof the alkyl group can optionally be substituted with a hydroxyl group(OH), an alkoxy group, halide, etc. Depending upon the groups that areselected, a first group can be incorporated within second group or,alternatively, the first group can be pendant (i.e., attached) or fusedto the second group.

Unless stated to the contrary, a formula with chemical bonds shown onlyas solid lines and not as wedges or dashed lines contemplates eachpossible isomer, e.g., each enantiomer and diastereomer, and a mixtureof isomers, such as a racemic or scalemic mixtures.

Reference will now be made in detail to specific aspects of thedisclosed materials, compounds, compositions, components, devices,articles, and methods, examples of which are illustrated in thefollowing description and examples, and in the figures and theirprevious and following description.

Compositions

Disclosed herein, in one aspect, are antimicrobial compositions. Thedisclosed antimicrobial compositions can be used to treat poultry andmeat tissue, as well as other foods, against various microorganisms.

The materials and components that can be used for, can be used inconjunction with, can be used in preparation for, or are products of thedisclosed compositions and methods are disclosed herein, and it isunderstood that when combinations, subsets, interactions, groups, etc.of these materials are disclosed that while specific reference of eachvarious individual and collective combinations and permutation of thesecompounds may not be explicitly disclosed, each is specificallycontemplated and described herein. For example, if a molecule isdisclosed and a number of modifications that can be made to a number ofsubstituents are discussed, each and every combination and permutationthat are possible are specifically contemplated unless specificallyindicated to the contrary. In another example, if a composition isdisclosed and a number of modifications that can be made to a number ofcomponents in the composition are discussed, each and every combinationand permutation that are possible are specifically contemplated unlessspecifically indicated to the contrary. Thus, if a class of substituentsor components A, B, and C are disclosed as well as a class ofsubstituents or components D, E, and F and an example of a combinationmolecule or combination composition, A-D is disclosed, then even if eachis not individually recited, each is individually and collectivelycontemplated. Thus, in this example, each of the combinations A-E, A-F,B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated andshould be considered disclosed from disclosure of A, B, and C; D, E, andF; and the example combination A-D. Likewise, any subset or combinationof these is also specifically contemplated and disclosed. Thus, forexample, the sub-group of A-E, B-F, and C-E are specificallycontemplated and should be considered disclosed from disclosure of A, B,and C; D, E, and F; and the example combination A-D. This conceptapplies to all aspects of this disclosure including, but not limited to,steps in methods of making and using the disclosed compositions. Thus,if there are a variety of additional steps that can be performed it isunderstood that each of these additional steps can be performed with anyspecific embodiment or combination of embodiments of the disclosedmethods, and that each such combination is specifically contemplated andshould be considered disclosed.

The disclosed antimicrobial compositions, in one aspect, comprise analiphatic heteroaryl salt, trichloromelamine, an at least two ammoniumsalts comprising an aliphatic benzylalkyl ammonium salt, a dialiphaticdialkyl ammonium salt, or a tetraalkyl ammonium salt. For example, thedisclosed antimicrobial compositions can comprise an aliphaticheteroaryl salt, trichloromelamine, an aliphatic benzylalkyl ammoniumsalt, and a tetraalkyl ammonium salt. In another example, the disclosedantimicrobial compositions can comprise an aliphatic heteroaryl salt,trichloromelamine, a dialiphatic dialkyl ammonium salt, and a tetraalkylammonium salt. In a still further example, the disclosed antimicrobialcompositions can comprise an aliphatic heteroaryl salt,trichloromelamine, an aliphatic benzylalkyl ammonium salt, and adialiphatic dialkyl ammonium salt.

Aliphatic Heteroaryl Salt

The aliphatic heteroaryl salt component of the disclosed antimicrobialcompositions can be one or more aliphatic heteroaryl salts. An aliphaticheteroaryl salt is a compound that comprises an aliphatic moiety bondedto a heteroaryl moiety, and a counterion, as are defined herein. One ormore types of aliphatic heteroaryl salts can be used in theantimicrobial compositions disclosed herein.

Aliphatic Moiety

In the aliphatic heteroaryl salt component of the disclosedantimicrobial compositions, the aliphatic moiety can be any alkyl,alkenyl, alkynyl, cycloalkyl, or cycloalkenyl group, as describedherein. Generally, the aliphatic moiety can comprise at least 10, atleast 12, at least 14, at least 16, at least 18, or at least 20 carbonatoms. In other examples, the aliphatic moiety can comprise a mixture ofaliphatic groups having a range of carbon atoms. For example, thealiphatic moiety can comprise from 10 to 40, from 12 to 38, from 14 to36, from 16 to 34, from 18 to 32, from 14 to 18, or from 20 to 30 carbonatoms. In some specific examples, the aliphatic moiety can contain 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28,29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, or 45carbon atoms, where any of the stated values can form an upper or lowerendpoint when appropriate. Examples of specific aliphatic moieties thatcan be used in the disclosed aliphatic heteroaryl salts include, but arenot limited to, decyl, dodecyl (lauryl), tetradecyl (myristyl),hexadecyl (palmityl or cetyl), octadecyl (stearyl), eicosyl (arachidyl),and linolenyl groups, including branched derivatives thereof and anymixtures thereof. In the aliphatic heteroaryl salts, the aliphaticmoiety is bonded to a heteroatom in the heteroaryl moiety.

Heteroaryl Moiety

In the aliphatic heteroaryl salt component of the disclosedantimicrobial compositions, the heteroaryl moiety can be any heteroarylmoiety as described herein. For example, the heteroaryl moiety can be anaryl group having one or more heteroatoms. Examples of specificheteroaryl moieties that can be used in the aliphatic heteroaryl saltsinclude, but are not limited to, pyrazole, pyridine, pyrazine,pyrimidine, pryidazine, indolizine, isoindole, indole, indazole,imidazole, oxazole, triazole, thiazole, purine, isoquinoline, quinoline,phthalazine, quinooxaline, phenazine, and the like, includingsubstituted derivatives and mixtures thereof.

In the aliphatic heteroaryl salts, a heteroatom in the heteroaryl moietyis bonded to the aliphatic moiety. When the heteroatom is nitrogen, thisforms a quaternary ammonium species.

Counterion

In the disclosed aliphatic heteroaryl salts, the counterion can be anyion that has an opposite charge as the remaining aliphatic heteroarylportion of the salt. For example, when the heteroatom of heteroarylmoiety is bonded to the aliphatic moiety to form a positively chargedquaternary ammonium moiety, the counterion can be a negatively chargedmoiety. Likewise, if the aliphatic heteroaryl portion is negativelycharged, then the counterion can be positively charged. In the disclosedaliphatic heteroaryl salts, one or more different types of counterionscan be present.

In some specific examples, the counterion can be a halide, such as afluoride, chloride, bromide, or iodide. In other examples, suitablecounterions for the aliphatic heteroaryl salt can include, but are notlimited to, sulfide, sulfates, sulfites, phosphide, phosphates,phosphites, carbonates, bicarbonates, nitrates, nitrites, hypochlorite,chlorite, perchlorate, acetate, formate, hydroxide, and the like,including mixtures thereof.

Specific Examples

In one aspect, the aliphatic heteroaryl salt can have any of thealiphatic moieties disclosed above combined with any of the heteroarylmoieties disclosed above. In some specific examples, the aliphaticheteroaryl salt can be an alkyl pyridinium salt, an alkyl quinoliniumsalt, an alkyl imidazolinium salt, or any mixture thereof. In otherexamples, the aliphatic heteroaryl salt can be an alkenyl pyrazoliumsalt, an alkenyl pyrazinium salt, an alkenyl quinolinium salt, or anymixture thereof. The counter ions for these specific examples can behalides, nitrates, sulfates, carbonates or any other counteriondisclosed herein. In other aspects, a specific example of an alkylpyridinium salt includes an alkyl pyridinium halide such as, but notlimited to, cetylpyridinium halide (e.g., cetylpyridinium chloride,cetylpyridinium bromide, or mixtures thereof), laurylpyridinium halide(e.g., laurylpyridinium chloride, laurylpyridinium bromide, or mixturesthereof), myristylpyridinium halide (e.g., myristylpyridinium chloride,myristylpyridinium bromide, or mixtures thereof), stearylpyridiniumhalide (e.g., stearylpyridinium chloride, stearylpyridinium bromide, ormixtures thereof), and arachidylpyridinium halide (arachidylpyridiniumchloride, arachidylpyridinium bromide, or mixtures thereof). In aspecific example, the aliphatic heteroaryl salt can comprisecetylpyridinium chloride, cetylpyridinium bromide, or a mixture thereof.

Amounts

The aliphatic heteroaryl salts disclosed herein can be prepared bymethods known in the art or can be obtained from commercial sources. Thealiphatic heteroaryl salt can be present in the antimicrobialcompositions disclosed herein in an amount of from less than about 20weight %, less than about 15 weight %, less than about 10 weight %, lessthan about 8 weight %, less than about 6 weight %, less than about 5weight %, less than about 4 weight %, less than about 3 weight %, lessthan about 2 weight %, less than about 1 weight %, or less than about0.5 weight %, based on the total weight of the antimicrobialcomposition. In another aspect, the aliphatic heteroaryl salt can bepresent in the antimicrobial compositions disclosed herein in an amountof from greater than about 0.5 weight %, greater than about 1 weight %,greater than about 2 weight %, greater than about 3 weight %, greaterthan about 4 weight %, greater than about 5 weight %, greater than about6 weight %, greater than about 8 weight %, greater than about 10 weight%, greater than about 15 weight %, or greater than about 20 weight %,based on the total weight of the antimicrobial composition. In stillanother aspect, the aliphatic heteroaryl salt can be present in theantimicrobial compositions disclosed herein in an amount of from about0.5 to about 20 weight %, from about 1 to about 15 weight %, from about2 to about 10 weight %, from about 3 to about 8 weight %, from about 3.5to about 8 weight %, from about 4 to about 6 weight %, from about 6 toabout 8 weight %, or about 7.5 weight %, based on the total weight ofthe antimicrobial composition. In yet another aspect, the aliphaticheteroaryl salt can be present in the antimicrobial compositionsdisclosed herein in an amount of about 0.25, 0.5, 0.75, 1.0, 1.25, 1.5,1.75, 2.0, 2.25, 2.5, 2.75, 3.0, 3.25, 3.5, 3.75, 4.0, 4.25, 4.5, 4.75,5.0, 5.25, 5.5, 5.75, 6.0, 6.25, 6.5, 6.75, 7.0, 7.25, 7.5, 7.75, 8.0,8.25, 8.5, 8.75, 9.0, 9.25, 9.5, 9.75, 10.0, 10.25. 10.5, 10.75, 11.0,11.25, 11.5, 11.75, 12.0, 12.25, 12.5, 12.75, 13.0, 13.25, 13.5, 13.75,14.0, 14.25, 14.5, 14.75, 15.0, 15.25, 15.5, 15.75, 16.0, 16.25, 16.5,16.75, 17.0, 17.25, 17.5, 17.75, 18.0, 18.25, 18.5, 18.75, 19.0, 19.25,19.5, 19.75, or 20.0 weight %, based on the total weight of theantimicrobial composition and where any of the stated values can form anupper or lower endpoint when appropriate.

In another aspect, the antimicrobial compositions disclosed herein cancontain less than about 20 parts by weight, less than about 15 parts byweight, less than about 10 parts by weight, less than about 8 parts byweight, less than about 6 parts by weight, less than about 5 parts byweight, less than about 4 parts by weight, less than about 3 parts byweight, less than about 2 parts by weight, less than about 1 part byweight, or less than about 0.5 parts by weight of the aliphaticheteroaryl salt. In another aspect, the antimicrobial compositionsdisclosed herein can contain greater than about 0.5 parts by weight,greater than about 1 part by weight, greater than about 2 parts byweight, greater than about 3 parts by weight, greater than about 4 partsby weight, greater than about 5 parts by weight, greater than about 6parts by weight, greater than about 8 parts by weight, greater thanabout 10 parts by weight, greater than about 15 parts by weight, orgreater than about 20 parts by weight of the aliphatic heteroaryl salt.In still another aspect, the antimicrobial compositions disclosed hereincan contain from about 0.5 to about 20 parts by weight, from about 1 toabout 15 parts by weight, from about 2 to about 10 parts by weight, fromabout 3 to about 8 parts by weight, from about 3.5 to about 8 parts byweight, from about 4 to about 6 parts by weight, from about 6 to about 8parts by weight, or about 7.5 parts by weight of the aliphaticheteroaryl salt. In yet another aspect, the antimicrobial compositionsdisclosed herein can contain about 0.25, 0.5, 0.75, 1.0, 1.25, 1.5,1.75, 2.0, 2.25, 2.5, 2.75, 3.0, 3.25, 3.5, 3.75, 4.0, 4.25, 4.5, 4.75,5.0, 5.25, 5.5, 5.75, 6.0, 6.25, 6.5, 6.75, 7.0, 7.25, 7.5, 7.75, 8.0,8.25, 8.5, 8.75, 9.0, 9.25, 9.5, 9.75, 10.0, 10.25. 10.5, 10.75, 11.0,11.25, 11.5, 11.75, 12.0, 12.25, 12.5, 12.75, 13.0, 13.25, 13.5, 13.75,14.0, 14.25, 14.5, 14.75, 15.0, 15.25, 15.5, 15.75, 16.0, 16.25, 16.5,16.75, 17.0, 17.25, 17.5, 17.75, 18.0, 18.25, 18.5, 18.75, 19.0, 19.25,19.5, 19.75, or 20.0 parts by weight of the aliphatic heteroaryl salt,where any of the stated values can form an upper or lower endpoint whenappropriate.

Trichloromelamine

The trichloromelamine (i.e.,N²,N⁴,N⁶-Trichloro-2,4,6-triamino-s-triazine) component of the disclosedantimicrobial compositions can be prepared by methods known in the artor can be obtained from commercial sources. Trichloromelamine can bepresent in the antimicrobial compositions disclosed herein in any amountas is described above for the aliphatic benzylalkyl ammonium salt. Forexample, trichloromelamine can be present in an amount of from in anamount of from less than about 1.0 weight %, less than about 0.75 weight%, less than about 0.5 weight %, less than about 0.25 weight %, lessthan about 0.10 weight %, less than about 0.075 weight %, less thanabout 0.05 weight %, less than about 0.025 weight %, less than about0.01 weight %, less than about 0.0075 weight %, less than about 0.005weight %, less than about 0.0025 weight %, or less than about 0.001weight %, based on the total weight of the antimicrobial composition. Inanother aspect, trichloromelamine can be present in the antimicrobialcompositions disclosed herein in an amount of from greater than about0.001 weight %, greater than about 0.0025 weight %, greater than about0.005 weight %, greater than about 0.0075 weight %, greater than about0.01 weight %, greater than about 0.025 weight %, greater than about0.05 weight %, greater than about 0.075 weight %, greater than about 0.1weight %, greater than about 0.25 weight %, greater than about 0.5weight %, greater than about 0.75 weight %, or greater than about 1.0weight %, based on the total weight of the antimicrobial composition. Instill another aspect, trichloromelamine can be present in theantimicrobial compositions disclosed herein in an amount of from about0.001 to about 1.0 weight %, from about 0.0025 to about 0.75 weight %,from about 0.005 to about 0.5 weight %, 0.005 to about 0.1 weight %,from about 0.0075 to about 0.25 weight %, from about 0.01 to about 0.1weight %, from about 0.025 to about 0.075 weight %, about 0.005 to about0.1 weight %, about 0.005 to about 0.02 weight %, about 0.005 to about0.01 weight %, or about 0.01 weight %, based on the total weight of theantimicrobial composition. Still further, trichloromelamine can bepresent in an amount of from about 0.001 to about 0.1 weight %, fromabout 0.005 to about 0.075 weight %, from about 0.0075 about 0.05 weight%, or from about 0.01 to about 0.02 weight %, based on the total weightof the antimicrobial composition. In yet another aspect,trichloromelamine can be present in the antimicrobial compositionsdisclosed herein in an amount of about 0.001, 0.0015, 0.002, 0.0025,0.003, 0.0035, 0.004, 0.0045, 0.005, 0.005, 0.0055, 0.006, 0.0065,0.007, 0.0075, 0.008, 0.0085, 0.009, 0.009, 0.0095, 0.01, 0.0105, 0.011,0.0115, 0.012, 0.0125, 0.013, 0.013, 0.0135, 0.014, 0.0145, 0.015,0.0155, 0.016, 0.0165, 0.017, 0.017, 0.0175, 0.018, 0.0185, 0.019,0.0195, 0.02, 0.0205, 0.021, 0.021, 0.0215, 0.022, 0.0225, 0.023,0.0235, 0.024, 0.0245, 0.025, 0.025, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08,0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 weight %, basedon the total weight of the antimicrobial composition and where any ofthe stated values can form an upper or lower endpoint when appropriate.

In another examples, the disclosed antimicrobial compositions cancontain less than about 1.0 parts by weight, less than about 0.75 partsby weight, less than about 0.5 parts by weight, less than about 0.25parts by weight, less than about 0.10 parts by weight, less than about0.075 parts by weight, less than about 0.05 parts by weight, less thanabout 0.025 parts by weight, less than about 0.01 parts by weight, lessthan about 0.0075 parts by weight, less than about 0.005 parts byweight, less than about 0.0025 parts by weight, or less than about 0.001parts by weight of trichloromelamine. In another aspect, theantimicrobial compositions disclosed herein can contain greater thanabout 0.001 parts by weight, greater than about 0.0025 parts by weight,greater than about 0.005 parts by weight, greater than about 0.0075parts by weight, greater than about 0.01 parts by weight, greater thanabout 0.025 parts by weight, greater than about 0.05 parts by weight,greater than about 0.075 parts by weight, greater than about 0.1 partsby weight, greater than about 0.25 parts by weight, greater than about0.5 parts by weight, greater than about 0.75 parts by weight, or greaterthan about 1.0 parts by weight of trichloromelamine. In still anotheraspect, the antimicrobial compositions disclosed herein can contain fromabout 0.001 to about 1.0 parts by weight, from about 0.0025 to about0.75 parts by weight, from about 0.005 to about 0.5 parts by weight,0.005 to about 0.1 parts by weight, from about 0.0075 to about 0.25parts by weight, from about 0.01 to about 0.1 parts by weight, fromabout 0.025 to about 0.075 parts by weight, about 0.005 to about 0.1parts by weight, about 0.005 to about 0.02 parts by weight, about 0.005to about 0.01 parts by weight, or about 0.01 parts by weight oftrichloromelamine. Still further, trichloromelamine can be present in anamount of from about 0.001 to about 0.1 parts by weight, from about0.005 to about 0.075 parts by weight, from about 0.0075 about 0.05 partsby weight, or from about 0.01 to about 0.02 parts by weighttrichloromelamine. In yet another aspect, the antimicrobial compositionsdisclosed herein can contain about 0.001, 0.0015, 0.002, 0.0025, 0.003,0.0035, 0.004, 0.0045, 0.005, 0.005, 0.0055, 0.006, 0.0065, 0.007,0.0075, 0.008, 0.0085, 0.009, 0.009, 0.0095, 0.01, 0.0105, 0.011,0.0115, 0.012, 0.0125, 0.013, 0.013, 0.0135, 0.014, 0.0145, 0.015,0.0155, 0.016, 0.0165, 0.017, 0.017, 0.0175, 0.018, 0.0185, 0.019,0.0195, 0.02, 0.0205, 0.021, 0.021, 0.0215, 0.022, 0.0225, 0.023,0.0235, 0.024, 0.0245, 0.025, 0.025, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08,0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 parts by weightof trichloromelamine, where any of the stated values can form an upperor lower endpoint when appropriate.

Ammonium Salts

As noted previously, in addition to the aliphatic heteroaryl salt andtrichloromelamine, the disclosed antimicrobial compositions can compriseat least two ammonium salts comprising aliphatic benzylalkyl ammoniumsalt, dialiphatic dialkyl ammonium salt, or tetraalkyl ammonium salt.

Aliphatic Benzylalkyl Ammonium Salt

The aliphatic benzylalkyl ammonium salt component of the disclosedantimicrobial compositions can be one or more aliphatic benzylalkylammonium salts. An aliphatic benzylalkyl ammonium salt is a compoundthat comprises an aliphatic moiety bonded to the nitrogen atom of abenzylalkyl amine moiety, and a counterion, as are defined herein. Thealiphatic moiety and counterion can be as described above. Thebenzylalkyl amine moiety can be a benzyl amine where the amine is bondedto an alkyl or cyclic alkyl group, as described above. One or more typesof aliphatic benzylalkyl ammonium salts can be used in the antimicrobialcompositions disclosed herein. The aliphatic benzylalkyl ammonium saltssuitable for use herein can be prepared by methods known in the art orcan be obtained from commercial sources.

In one aspect, the aliphatic benzylalkyl ammonium salt can berepresented by the following formula:

wherein R¹ is an aliphatic group, as described above, R² and R³ are,independent of one another, alkyl groups or cyclic alkyl groups asdescribed herein, and X is a counterion as described herein. In someexamples, one or more of the “R” substituents can be a long chain alkylgroup (e.g., the number of carbon atoms is greater than 6). In otherexamples, one or more of the “R” substituents can be a short chain alkylgroup (e.g., the number of carbon atoms is 6 or less). In still otherexamples, one of the “R” substituents is a long chain alkyl group andthe other two “R” substituents are short chain alkyl groups.

Specific Examples

In one aspect, the aliphatic benzylalkyl ammonium salt can have any ofthe aliphatic moieties disclosed above bonded to any benzylalkyl aminemoieties disclosed above. In some specific examples, R¹ in the formulaof aliphatic benzylalkyl ammonium salts can be an aliphatic group offrom 10 to 40 carbon atoms, e.g., a decyl, dodecyl (lauryl), tetradecyl(myristyl), hexadecyl (palmityl or cetyl), octadecyl (stearyl), oreicosyl (arachidyl) group, and R² and R³ can each be, independent of oneanother, a methyl, ethyl, propyl, butyl, pentyl, or hexyl group.

In another aspect, the aliphatic benzylalkyl ammonium salts can include,but are not limited to, alkyl dimethyl benzyl ammonium halides (e.g.,alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammoniumbromide, or mixtures thereof). Specific examples of alkyl dimethylbenzyl ammonium halides include, but are not limited to, cetyl dimethylbenzyl ammonium halide (e.g., cetyl dimethyl benzyl ammonium chloride,cetyl dimethyl benzyl ammonium chloride bromide, or mixtures thereof),lauryl dimethyl benzyl ammonium halide (e.g., lauryl dimethyl benzylammonium chloride, lauryl dimethyl benzyl ammonium bromide, or mixturesthereof), myristyl dimethyl benzyl ammonium halide (e.g., myristyldimethyl benzyl ammonium chloride, myristyl dimethyl benzyl ammoniumbromide, or mixtures thereof), stearyl dimethyl benzyl ammonium halide(e.g., stearyl dimethyl benzyl ammonium chloride, stearyl dimethylbenzyl ammonium bromide, or mixtures thereof), and arachidyl dimethylbenzyl ammonium halide (e.g., arachidyl dimethyl benzyl ammoniumchloride, arachidyl dimethyl benzyl ammonium bromide, or mixturesthereof).

In yet another aspect, the aliphatic benzylalkyl ammonium salts caninclude, but are not limited to, alkyl methylethyl benzyl ammoniumhalides. Specific examples of alkyl methylethyl benzyl ammonium halidesinclude, but are not limited to, cetyl methylethyl benzyl ammoniumhalide (e.g., cetyl methylethyl benzyl ammonium chloride, cetylmethylethyl benzyl ammonium chloride bromide, or mixtures thereof),lauryl methylethyl benzyl ammonium halide (e.g., lauryl methylethylbenzyl ammonium chloride, lauryl methylethyl benzyl ammonium bromide, ormixtures thereof), myristyl methylethyl benzyl ammonium halide (e.g.,myristyl methylethyl benzyl ammonium chloride, myristyl methylethylbenzyl ammonium bromide, or mixtures thereof), stearyl methylethylbenzyl ammonium halide (e.g., stearyl methylethyl benzyl ammoniumchloride, stearyl methylethyl benzyl ammonium bromide, or mixturesthereof), and arachidyl methylethyl benzyl ammonium halide (e.g.,arachidyl methylethyl benzyl ammonium chloride, arachidyl methylethylbenzyl ammonium bromide, or mixtures thereof).

Amounts

The aliphatic benzylalkyl ammonium salts disclosed herein can beprepared by methods known in the art or can be obtained from commercialsources. The aliphatic benzylalkyl ammonium salt can be present in thedisclosed antimicrobial compositions in an amount of from less thanabout 1.0 weight %, less than about 0.75 weight %, less than about 0.5weight %, less than about 0.25 weight %, less than about 0.10 weight %,less than about 0.075 weight %, less than about 0.05 weight %, less thanabout 0.025 weight %, less than about 0.01 weight %, less than about0.0075 weight %, less than about 0.005 weight %, less than about 0.0025weight %, or less than about 0.001 weight %, based on the total weightof the antimicrobial composition. In another aspect, the aliphaticbenzylalkyl ammonium salt can be present in the antimicrobialcompositions disclosed herein in an amount of from greater than about0.001 weight %, greater than about 0.0025 weight %, greater than about0.005 weight %, greater than about 0.0075 weight %, greater than about0.01 weight %, greater than about 0.025 weight %, greater than about0.05 weight %, greater than about 0.075 weight %, greater than about 0.1weight %, greater than about 0.25 weight %, greater than about 0.5weight %, greater than about 0.75 weight %, or greater than about 1.0weight %, based on the total weight of the antimicrobial composition. Instill another aspect, the aliphatic benzylalkyl ammonium salt can bepresent in the antimicrobial compositions disclosed herein in an amountof from about 0.001 to about 1.0 weight %, from about 0.0025 to about0.75 weight %, from about 0.005 to about 0.5 weight %, 0.005 to about0.1 weight %, from about 0.0075 to about 0.25 weight %, from about 0.01to about 0.1 weight %, from about 0.025 to about 0.075 weight %, about0.005 to about 0.1 weight %, about 0.005 to about 0.02 weight %, about0.005 to about 0.01 weight %, or about 0.01 weight %, based on the totalweight of the antimicrobial composition. Still further, the aliphaticbenzylalkyl ammonium salt can be present in an amount of from about0.001 to about 0.1 weight %, from about 0.005 to about 0.075 weight %,from about 0.0075 about 0.05 weight %, or from about 0.01 to about 0.02weight %, based on the total weight of the antimicrobial composition. Inyet another aspect, the aliphatic benzylalkyl ammonium salt can bepresent in the antimicrobial compositions disclosed herein in an amountof about 0.001, 0.0015, 0.002, 0.0025, 0.003, 0.0035, 0.004, 0.0045,0.005, 0.005, 0.0055, 0.006, 0.0065, 0.007, 0.0075, 0.008, 0.0085,0.009, 0.009, 0.0095, 0.01, 0.0105, 0.011, 0.0115, 0.012, 0.0125, 0.013,0.013, 0.0135, 0.014, 0.0145, 0.015, 0.0155, 0.016, 0.0165, 0.017,0.017, 0.0175, 0.018, 0.0185, 0.019, 0.0195, 0.02, 0.0205, 0.021, 0.021,0.0215, 0.022, 0.0225, 0.023, 0.0235, 0.024, 0.0245, 0.025, 0.025, 0.03,0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7,0.8, 0.9, or 1 weight %, based on the total weight of the antimicrobialcomposition and where any of the stated values can form an upper orlower endpoint when appropriate.

In another aspect, the disclosed antimicrobial compositions can containless than about 1.0 parts by weight, less than about 0.75 parts byweight, less than about 0.5 parts by weight, less than about 0.25 partsby weight, less than about 0.10 parts by weight, less than about 0.075parts by weight, less than about 0.05 parts by weight, less than about0.025 parts by weight, less than about 0.01 parts by weight, less thanabout 0.0075 parts by weight, less than about 0.005 parts by weight,less than about 0.0025 parts by weight, or less than about 0.001 partsby weight of the aliphatic benzylalkyl ammonium salt. In another aspect,the antimicrobial compositions disclosed herein can contain greater thanabout 0.001 parts by weight, greater than about 0.0025 parts by weight,greater than about 0.005 parts by weight, greater than about 0.0075parts by weight, greater than about 0.01 parts by weight, greater thanabout 0.025 parts by weight, greater than about 0.05 parts by weight,greater than about 0.075 parts by weight, greater than about 0.1 partsby weight, greater than about 0.25 parts by weight, greater than about0.5 parts by weight, greater than about 0.75 parts by weight, or greaterthan about 1.0 parts by weight of the aliphatic benzylalkyl ammoniumsalt. In still another aspect, the antimicrobial compositions disclosedherein can contain from about 0.001 to about 1.0 parts by weight, fromabout 0.0025 to about 0.75 parts by weight, from about 0.005 to about0.5 parts by weight, 0.005 to about 0.1 parts by weight, from about0.0075 to about 0.25 parts by weight, from about 0.01 to about 0.1 partsby weight, from about 0.025 to about 0.075 parts by weight, about 0.005to about 0.1 parts by weight, about 0.005 to about 0.02 parts by weight,about 0.005 to about 0.01 parts by weight, or about 0.01 parts by weightof the aliphatic benzylalkyl ammonium salt. Still further, the aliphaticbenzylalkyl ammonium salt can be present in an amount of from about0.001 to about 0.1 parts by weight, from about 0.005 to about 0.075parts by weight, from about 0.0075 about 0.05 parts by weight, or fromabout 0.01 to about 0.02 parts by weight. In yet another aspect, theantimicrobial compositions disclosed herein can contain about 0.001,0.0015, 0.002, 0.0025, 0.003, 0.0035, 0.004, 0.0045, 0.005, 0.005,0.0055, 0.006, 0.0065, 0.007, 0.0075, 0.008, 0.0085, 0.009, 0.009,0.0095, 0.01, 0.0105, 0.011, 0.0115, 0.012, 0.0125, 0.013, 0.013,0.0135, 0.014, 0.0145, 0.015, 0.0155, 0.016, 0.0165, 0.017, 0.017,0.0175, 0.018, 0.0185, 0.019, 0.0195, 0.02, 0.0205, 0.021, 0.021,0.0215, 0.022, 0.0225, 0.023, 0.0235, 0.024, 0.0245, 0.025, 0.025, 0.03,0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7,0.8, 0.9, or 1 parts by weight of the aliphatic benzylalkyl ammoniumsalt, where any of the stated values can form an upper or lower endpointwhen appropriate.

Dialiphatic Dialkyl Ammonium Salts

The dialiphatic dialkyl ammonium salt component of the disclosedantimicrobial compositions can be one or more dialiphatic dialkylammonium salt. A dialiphatic dialkyl ammonium salt is a compound thatcomprises two aliphatic moieties and two alkyl moieties bonded to anitrogen atom, and a counterion, as are defined herein. The aliphaticmoieties can be the same or different and can be any aliphatic group asdescribed above. The alkyl moieties can be the same or different can beany alkyl group as described above. The counterion can also be asdescribed above. In the disclosed dialiphatic dialkyl ammoniums salts,the two aliphatic moieties can have more than 10 carbon atoms and thetwo alkyl moieties can have less than 10 carbon atoms. In anotheralternative, the two aliphatic moieties can have less than 10 carbonatoms and the two alkyl moieties can have more than 10 carbon atoms. Oneor more types of dialiphatic dialkyl ammonium salts can be used in theantimicrobial compositions disclosed herein.

In some particular examples, the dialiphatic dialkyl ammonium salt canbe di-dodecyl dimethyl ammonium chloride or bromide, di-tetradecyldimethyl ammonium chloride or bromide, dihexadecyl dimethyl ammoniumchloride or bromide, and the like, including combinations thereof.

Amounts

The dialiphatic dialkyl ammonium salts disclosed herein can be preparedby methods known in the art or can be obtained from commercial sources.The dialiphatic dialkyl ammonium salt can be present in the disclosedantimicrobial compositions in an amount of from less than about 1.0weight %, less than about 0.75 weight %, less than about 0.5 weight %,less than about 0.25 weight %, less than about 0.10 weight %, less thanabout 0.075 weight %, less than about 0.05 weight %, less than about0.025 weight %, less than about 0.01 weight %, less than about 0.0075weight %, less than about 0.005 weight %, less than about 0.0025 weight%, or less than about 0.001 weight %, based on the total weight of theantimicrobial composition. In another aspect, the dialiphatic dialkylammonium salt can be present in the antimicrobial compositions disclosedherein in an amount of from greater than about 0.001 weight %, greaterthan about 0.0025 weight %, greater than about 0.005 weight %, greaterthan about 0.0075 weight %, greater than about 0.01 weight %, greaterthan about 0.025 weight %, greater than about 0.05 weight %, greaterthan about 0.075 weight %, greater than about 0.1 weight %, greater thanabout 0.25 weight %, greater than about 0.5 weight %, greater than about0.75 weight %, or greater than about 1.0 weight %, based on the totalweight of the antimicrobial composition. In still another aspect, thedialiphatic dialkyl ammonium salt can be present in the antimicrobialcompositions disclosed herein in an amount of from about 0.001 to about1.0 weight %, from about 0.0025 to about 0.75 weight %, from about 0.005to about 0.5 weight %, 0.005 to about 0.1 weight %, from about 0.0075 toabout 0.25 weight %, from about 0.01 to about 0.1 weight %, from about0.025 to about 0.075 weight %, about 0.005 to about 0.1 weight %, about0.005 to about 0.02 weight %, about 0.005 to about 0.01 weight %, orabout 0.01 weight %, based on the total weight of the antimicrobialcomposition. Still further, the dialiphatic dialkyl ammonium salt can bepresent in an amount of from about 0.001 to about 0.1 weight %, fromabout 0.005 to about 0.075 weight %, from about 0.0075 about 0.05 weight%, or from about 0.01 to about 0.02 weight %, based on the total weightof the antimicrobial composition. In yet another aspect, the dialiphaticdialkyl ammonium salt can be present in the antimicrobial compositionsdisclosed herein in an amount of about 0.001, 0.0015, 0.002, 0.0025,0.003, 0.0035, 0.004, 0.0045, 0.005, 0.005, 0.0055, 0.006, 0.0065,0.007, 0.0075, 0.008, 0.0085, 0.009, 0.009, 0.0095, 0.01, 0.0105, 0.011,0.0115, 0.012, 0.0125, 0.013, 0.013, 0.0135, 0.014, 0.0145, 0.015,0.0155, 0.016, 0.0165, 0.017, 0.017, 0.0175, 0.018, 0.0185, 0.019,0.0195, 0.02, 0.0205, 0.021, 0.021, 0.0215, 0.022, 0.0225, 0.023,0.0235, 0.024, 0.0245, 0.025, 0.025, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08,0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 weight %, basedon the total weight of the antimicrobial composition and where any ofthe stated values can form an upper or lower endpoint when appropriate.

In another aspect, the disclosed antimicrobial compositions can containless than about 1.0 parts by weight, less than about 0.75 parts byweight, less than about 0.5 parts by weight, less than about 0.25 partsby weight, less than about 0.10 parts by weight, less than about 0.075parts by weight, less than about 0.05 parts by weight, less than about0.025 parts by weight, less than about 0.01 parts by weight, less thanabout 0.0075 parts by weight, less than about 0.005 parts by weight,less than about 0.0025 parts by weight, or less than about 0.001 partsby weight of the dialiphatic dialkyl ammonium salt. In another aspect,the antimicrobial compositions disclosed herein can contain greater thanabout 0.001 parts by weight, greater than about 0.0025 parts by weight,greater than about 0.005 parts by weight, greater than about 0.0075parts by weight, greater than about 0.01 parts by weight, greater thanabout 0.025 parts by weight, greater than about 0.05 parts by weight,greater than about 0.075 parts by weight, greater than about 0.1 partsby weight, greater than about 0.25 parts by weight, greater than about0.5 parts by weight, greater than about 0.75 parts by weight, or greaterthan about 1.0 parts by weight of the dialiphatic dialkyl ammonium salt.In still another aspect, the antimicrobial compositions disclosed hereincan contain from about 0.001 to about 1.0 parts by weight, from about0.0025 to about 0.75 parts by weight, from about 0.005 to about 0.5parts by weight, 0.005 to about 0.1 parts by weight, from about 0.0075to about 0.25 parts by weight, from about 0.01 to about 0.1 parts byweight, from about 0.025 to about 0.075 parts by weight, about 0.005 toabout 0.1 parts by weight, about 0.005 to about 0.02 parts by weight,about 0.005 to about 0.01 parts by weight, or about 0.01 parts by weightof the dialiphatic dialkyl ammonium salt. Still further, the dialiphaticdialkyl ammonium salt can be present in an amount of from about 0.001 toabout 0.1 parts by weight, from about 0.005 to about 0.075 parts byweight, from about 0.0075 about 0.05 parts by weight, or from about 0.01to about 0.02 parts by weight. In yet another aspect, the antimicrobialcompositions disclosed herein can contain about 0.001, 0.0015, 0.002,0.0025, 0.003, 0.0035, 0.004, 0.0045, 0.005, 0.005, 0.0055, 0.006,0.0065, 0.007, 0.0075, 0.008, 0.0085, 0.009, 0.009, 0.0095, 0.01,0.0105, 0.011, 0.0115, 0.012, 0.0125, 0.013, 0.013, 0.0135, 0.014,0.0145, 0.015, 0.0155, 0.016, 0.0165, 0.017, 0.017, 0.0175, 0.018,0.0185, 0.019, 0.0195, 0.02, 0.0205, 0.021, 0.021, 0.0215, 0.022,0.0225, 0.023, 0.0235, 0.024, 0.0245, 0.025, 0.025, 0.03, 0.04, 0.05,0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or1 parts by weight of the dialiphatic dialkyl ammonium salt, where any ofthe stated values can form an upper or lower endpoint when appropriate.

Tetraalkyl Ammonium Salts

The tetraalkyl ammonium salt component of the disclosed antimicrobialcompositions can be one or more tetraalkyl ammonium salts. Suitabletetraalkyl ammonium salts comprise four alkyl moieties, as disclosedherein, and a counterion, also disclosed herein. In one example, atetraalkyl ammonium salt can comprise one long chain alkyl moiety (e.g.,greater than 10 carbon atoms in length) and three short chain alkylmoieties (e.g., 10 carbon atoms or less in length).

Some specific examples of tetraalkyl ammonium salts that can be includedin the disclosed antimicrobial compositions include, but are not limitedto, cetyl trimethyl ammonium halide (e.g., chloride or bromide), lauryltrimethyl ammonium halide (e.g., chloride or bromide), myristyltrimethyl ammonium halide (e.g., chloride or bromide), stearyl trimethylammonium halide (e.g., chloride or bromide), arachidyl trimethylammonium halide (e.g., chloride or bromide), or mixtures thereof. Otherexamples include, but are not limited to, cetyl dimethylethyl ammoniumbromide, lauryl dimethylethyl ammonium chloride, lauryl dimethylethylammonium bromide, myristyl dimethylethyl ammonium chloride, myristyldimethylethyl ammonium bromide, stearyl dimethylethyl ammonium chloride,stearyl dimethylethyl ammonium bromide, arachidyl dimethylethyl ammoniumchloride, arachidyl dimethylethyl ammonium bromide, or mixtures thereof.

Amounts

The tetraalkyl ammonium salts disclosed herein can be prepared bymethods known in the art or can be obtained from commercial sources. Thetetraalkyl ammonium salt can be present in the disclosed antimicrobialcompositions in an amount of from less than about 1.0 weight %, lessthan about 0.75 weight %, less than about 0.5 weight %, less than about0.25 weight %, less than about 0.10 weight %, less than about 0.075weight %, less than about 0.05 weight %, less than about 0.025 weight %,less than about 0.01 weight %, less than about 0.0075 weight %, lessthan about 0.005 weight %, less than about 0.0025 weight %, or less thanabout 0.001 weight %, based on the total weight of the antimicrobialcomposition. In another aspect, the tetraalkyl ammonium salt can bepresent in the antimicrobial compositions disclosed herein in an amountof from greater than about 0.001 weight %, greater than about 0.0025weight %, greater than about 0.005 weight %, greater than about 0.0075weight %, greater than about 0.01 weight %, greater than about 0.025weight %, greater than about 0.05 weight %, greater than about 0.075weight %, greater than about 0.1 weight %, greater than about 0.25weight %, greater than about 0.5 weight %, greater than about 0.75weight %, or greater than about 1.0 weight %, based on the total weightof the antimicrobial composition. In still another aspect, thetetraalkyl ammonium salt can be present in the antimicrobialcompositions disclosed herein in an amount of from about 0.001 to about1.0 weight %, from about 0.0025 to about 0.75 weight %, from about 0.005to about 0.5 weight %, 0.005 to about 0.1 weight %, from about 0.0075 toabout 0.25 weight %, from about 0.01 to about 0.1 weight %, from about0.025 to about 0.075 weight %, about 0.005 to about 0.1 weight %, about0.005 to about 0.02 weight %, about 0.005 to about 0.01 weight %, orabout 0.01 weight %, based on the total weight of the antimicrobialcomposition. Still further, the tetraalkyl ammonium salt can be presentin an amount of from about 0.001 to about 0.1 weight %, from about 0.005to about 0.075 weight %, from about 0.0075 about 0.05 weight %, or fromabout 0.01 to about 0.02 weight %, based on the total weight of theantimicrobial composition. In yet another aspect, the tetraalkylammonium salt can be present in the antimicrobial compositions disclosedherein in an amount of about 0.001, 0.0015, 0.002, 0.0025, 0.003,0.0035, 0.004, 0.0045, 0.005, 0.005, 0.0055, 0.006, 0.0065, 0.007,0.0075, 0.008, 0.0085, 0.009, 0.009, 0.0095, 0.01, 0.0105, 0.011,0.0115, 0.012, 0.0125, 0.013, 0.013, 0.0135, 0.014, 0.0145, 0.015,0.0155, 0.016, 0.0165, 0.017, 0.017, 0.0175, 0.018, 0.0185, 0.019,0.0195, 0.02, 0.0205, 0.021, 0.021, 0.0215, 0.022, 0.0225, 0.023,0.0235, 0.024, 0.0245, 0.025, 0.025, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08,0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 weight %, basedon the total weight of the antimicrobial composition and where any ofthe stated values can form an upper or lower endpoint when appropriate.

In another aspect, the disclosed antimicrobial compositions can containless than about 1.0 parts by weight, less than about 0.75 parts byweight, less than about 0.5 parts by weight, less than about 0.25 partsby weight, less than about 0.10 parts by weight, less than about 0.075parts by weight, less than about 0.05 parts by weight, less than about0.025 parts by weight, less than about 0.01 parts by weight, less thanabout 0.0075 parts by weight, less than about 0.005 parts by weight,less than about 0.0025 parts by weight, or less than about 0.001 partsby weight of the tetraalkyl ammonium salt. In another aspect, theantimicrobial compositions disclosed herein can contain greater thanabout 0.001 parts by weight, greater than about 0.0025 parts by weight,greater than about 0.005 parts by weight, greater than about 0.0075parts by weight, greater than about 0.01 parts by weight, greater thanabout 0.025 parts by weight, greater than about 0.05 parts by weight,greater than about 0.075 parts by weight, greater than about 0.1 partsby weight, greater than about 0.25 parts by weight, greater than about0.5 parts by weight, greater than about 0.75 parts by weight, or greaterthan about 1.0 parts by weight of the tetraalkyl ammonium salt. In stillanother aspect, the antimicrobial compositions disclosed herein cancontain from about 0.001 to about 1.0 parts by weight, from about 0.0025to about 0.75 parts by weight, from about 0.005 to about 0.5 parts byweight, 0.005 to about 0.1 parts by weight, from about 0.0075 to about0.25 parts by weight, from about 0.01 to about 0.1 parts by weight, fromabout 0.025 to about 0.075 parts by weight, about 0.005 to about 0.1parts by weight, about 0.005 to about 0.02 parts by weight, about 0.005to about 0.01 parts by weight, or about 0.01 parts by weight of thetetraalkyl ammonium salt. Still further, the tetraalkyl ammonium saltcan be present in an amount of from about 0.001 to about 0.1 parts byweight, from about 0.005 to about 0.075 parts by weight, from about0.0075 about 0.05 parts by weight, or from about 0.01 to about 0.02parts by weight. In yet another aspect, the antimicrobial compositionsdisclosed herein can contain about 0.001, 0.0015, 0.002, 0.0025, 0.003,0.0035, 0.004, 0.0045, 0.005, 0.005, 0.0055, 0.006, 0.0065, 0.007,0.0075, 0.008, 0.0085, 0.009, 0.009, 0.0095, 0.01, 0.0105, 0.011,0.0115, 0.012, 0.0125, 0.013, 0.013, 0.0135, 0.014, 0.0145, 0.015,0.0155, 0.016, 0.0165, 0.017, 0.017, 0.0175, 0.018, 0.0185, 0.019,0.0195, 0.02, 0.0205, 0.021, 0.021, 0.0215, 0.022, 0.0225, 0.023,0.0235, 0.024, 0.0245, 0.025, 0.025, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08,0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 parts by weightof the tetraalkyl ammonium salt, where any of the stated values can forman upper or lower endpoint when appropriate.

Additional Components

In addition to the components disclosed above, the disclosedantimicrobial compositions can be in the form of an aqueous solution;thus, water can be another component of the disclosed antimicrobialcompositions. Also, the disclosed antimicrobial compositions canoptionally include one or more additional components such as carriers,adjuvants, solubilizing agents, suspending agents, diluents,surfactants, other antimicrobial agents, preservatives, fillers, andadditives designed to affect the viscosity, thixotropy or ability of theantimicrobial composition to adhere to and/or penetrate tissue. In oneaspect, it can be desired that one or more of the additional componentsbe consumer acceptable. By “consumer acceptable” is meant a materialthat is not biologically or otherwise undesirable when consumed, e.g.,an agent that is acceptable when used in or on foods and beverages andwhich can be consumed by an individual (e.g., human, pet, livestock,etc.) along with the selected active components without causingsignificant undesirable biological effects or interacting in adeleterious manner with any of the other components of the compositionin which it is contained. For example, a consumer acceptable agent canbe any compound generally recognized as safe (GRAS). These additionalcomponents can be prepared by methods known in the art or obtained fromcommercial sources.

In one example, suitable additional components include surfactants suchas Triton X-100 (i.e., polyethylene glycolP-1,1,3,3-tetramethylbutylphenyl ether) for better cell penetration.

Carriers

In other examples, the antimicrobial compositions disclosed herein canfurther comprise a carrier. The term “carrier” means a compound,composition, substance, or structure that, when in combination with acompound or composition disclosed herein, aids or facilitatespreparation, storage, administration, delivery, effectiveness,selectivity, or any other feature of the compound or composition for itsintended use or purpose. For example, a carrier can be selected tominimize any degradation of the active components and to minimize anyadverse side effects. Examples of suitable aqueous and non-aqueouscarriers, diluents, solvents include water, ethanol, polyols(propyleneglycol, polyethyleneglycol, glycerol, and the like), vegetableoils, and suitable mixtures thereof.

Adjuvants

In a further example, the antimicrobial compositions disclosed hereincan also comprise adjuvants such as preserving, wetting, emulsifying,suspending agents, and dispensing agents. Prevention of the action ofother microorganisms can be accomplished by various antifungal agents,for example, parabens, chlorobutanol, phenol, organic acids (e.g.,sorbic acid, acetic acid, benzoic acid), and the like, includingmixtures thereof. It may also be desirable to include surfactants,binders, as for example, carboxymethylcellulose, alignates, gelatin,polyvinylpyrrolidone, sucrose, and acacia, humectants, as for example,glycerol, wetting agents, as for example, cetyl alcohol, and glycerolmonostearate, adsorbents, as for example, kaolin and bentonite, andlubricants, as for example, talc, calcium stearate, magnesium stearate,solid polyethylene glycols, sodium lauryl sulfate, or mixtures thereof.

Solubilizing and Suspending Agents

Suitable suspending agents can include, for example, ethoxylatedisostearyl alcohols, polyoxyethylene sorbitol and sorbitan esters,microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agarand tragacanth, or mixtures of these substances, and the like.

The disclosed antimicrobial compositions can also comprise solubilizingagents and emulsifiers, as for example, ethyl alcohol, isopropylalcohol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl alcohol,benzyl benzoate, propyleneglycol, 1,3-butyleneglycol, dimethylformamide,oils, in particular, cottonseed oil, groundnut oil, corn germ oil, oliveoil, castor oil and sesame oil, glycerol, tetrahydrofurfuryl alcohol,polyethyleneglycols and fatty acid esters of sorbitan or mixtures ofthese substances, and the like.

Additional Quaternary Ammonium Salts

In one aspect, the disclosed antimicrobial compositions can comprise oneor more additional quaternary ammonium salts. Other additionalquaternary ammonium salts that can be used in the disclosedantimicrobial compositions include, but are not limited to, otheraliphatic heteroaryl salts (e.g., alkyl pyridinium halides, alkylquinolinium halides, alkyl indolinium halides, and the like), aliphaticheterocyclic salts (e.g., aliphatic heterocycloalkyl salts like alkylpiperidinium salts or aliphatic heterocycloalkenyl salts), aliphaticbenzylalkyl ammoniums salts, dialiphatic dialkyl ammoniums salts, andtetraalkyl ammonium salts, and chloramine-T.

Amounts

The additional components disclosed herein can be present in thedisclosed antimicrobial compositions in any amount as is described abovefor the aliphatic benzylalkyl ammonium salts, dialiphatic dialkylammonium salts, tetraalkyl ammoniums salts, and/or trichlormelamine. Forexample, one or more additional components can be present in an amountof from about 0.001 to about 0.1 weight %, from about 0.005 to about0.075 weight %, from about 0.0075 about 0.05 weight %, from about 0.01to about 0.02 weight %, about 0.005 to about 0.1 weight %, about 0.005to about 0.02 weight %, about 0.005 to about 0.01 weight %, or about0.01 weight %, based on the total weight of the antimicrobialcomposition. In another example, the disclosed antimicrobialcompositions can contain from about 0.001 to about 0.1 parts by weight,from about 0.005 to about 0.075 parts by weight, from about 0.0075 about0.05 parts by weight, from about 0.01 to about 0.02 parts by weight,about 0.005 to about 0.1 parts by weight, about 0.005 to about 0.02parts by weight, about 0.005 to about 0.01 parts by weight, or about0.01 parts by weight, based of one or more additional components.

Exemplary Compositions

In one example, disclosed herein is an antimicrobial compositioncomprising an aliphatic heteroaryl salt, trichloromelamine, an aliphaticbenzylalkyl ammonium salt, and a tetraalkyl ammonium salt. For example,disclosed herein are antimicrobial compositions that consist essentiallyof an aliphatic heteroaryl salt, trichloromelamine, an aliphaticbenzylalkyl ammonium salt, and a tetraalkyl ammonium salt. “Consistingessentially of” is used herein to exclude additional components or theomission of components that would change the basic and novelcharacteristics of the composition; this is also meant to exclude theomission of aliphatic heteroaryl salts, trichloromelamine, aliphaticbenzylalkyl ammonium salts, dialiphatic dialkyl ammoniums salts, and/ortetraalkyl ammonium salts from the composition but not the addition oromission of other carriers, adjuvants, solubilizing and suspendingagents, and additional components as described herein. The compositioncan also comprise water.

In a further example, disclosed herein in an antimicrobial compositioncomprising an aliphatic heteroaryl salt, trichloromelamine, adialiphatic dialkyl ammonium salt, and a tetraalkyl ammonium salt. Forexample, disclosed herein are antimicrobial compositions that consistessentially of an aliphatic heteroaryl salt, trichloromelamine, adialiphatic dialkyl ammonium salt, and a tetraalkyl ammonium salt.

In a still further example, disclosed herein in an antimicrobialcomposition comprising an aliphatic heteroaryl salt, trichloromelamine,an aliphatic benzylalkyl ammonium salt, and a dialiphatic dialkylammonium salt. For example, disclosed herein are antimicrobialcompositions that consist essentially of an aliphatic heteroaryl salt,trichloromelamine, an aliphatic benzylalkyl ammonium salt, and adialiphatic dialkyl ammonium salt.

In the disclosed compositions, the aliphatic heteroaryl salt can be anyaliphatic heteroaryl salt disclosed herein, for example, analkylpyridinium halide. Such an alkylpyridinium halide can comprise, forexample, cetylpyridinium chloride, cetylpyridinium bromide, or a mixturethereof. The aliphatic benzylalkyl ammonium salt can be any aliphaticbenzylalkyl ammonium salt disclosed herein, for example, an alkyldimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammoniumbromide, or a mixture thereof. The dialiphatic dialkyl ammonium salt canbe any dialiphatic dialkyl ammonium salt disclosed herein, for example,di-dodecyl dimethyl ammonium chloride or bromide, di-tetradecyl dimethylammonium chloride or bromide, dihexadecyl dimethyl ammonium chloride orbromide, or mixtures thereof. The tetraalkyl ammonium salt can be anytetraalkyl ammonium salt disclosed herein, for example, cetyl trimethylammonium chloride or bromide, lauryl trimethyl ammonium chloride orbromide, myristyl trimethyl ammonium chloride or bromide, or mixturesthereof.

In one example, disclosed herein are antimicrobial compositionscomprising an aliphatic heteroaryl salt, trichloromelamine, and at leasttwo ammonium salts comprising an aliphatic benzylalkyl ammonium salt, adialiphatic dialkyl ammonium salt, or a tetraalkyl ammonium salt. Inanother example, disclosed herein are antimicrobial compositionscomprising an aliphatic heteroaryl salt, trichloromelamine, a tetraalkylammonium salt, and an ammonium salt comprising an aliphatic benzylalkylammonium salt or a dialiphatic dialkyl ammonium salt. In yet anotherexample, disclosed herein are antimicrobial compositions comprising analiphatic heteroaryl salt, trichloromelamine, a dialiphatic dialkylammonium salt, and an ammonium salt comprising an aliphatic benzylalkylammonium salt or a tetraalkyl ammonium salt. In still another example,disclosed herein are antimicrobial compositions comprising an aliphaticheteroaryl salt, trichloromelamine, an aliphatic benzylalkyl ammoniumsalt, and an ammonium salt comprising a tetraalkyl ammonium salt or adialiphatic dialkyl ammonium salt.

In these compositions, the aliphatic heteroaryl salt can be as disclosedabove; for example, it can comprise an alkylpyridinium halide asdisclosed herein (e.g., cetylpyridinium chloride, cetylpyridiniumbromide, or a mixture thereof). When the aliphatic benzylalkyl ammoniumsalt is present, it can be any aliphatic benzyalkyl ammonium saltdisclosed herein (e.g., alkyl dimethyl benzyl ammonium halide, alkyldimethyl benzyl ammonium halide, or a mixture thereof). When thedialiphatic dialkyl ammonium salt is present, it can be any dialiphaticdialkyl ammonium salt disclosed herein (e.g., didodecyl dimethylammonium halide, ditetradecyl dimethyl ammonium halide, dihexadecyldimethyl ammonium halide, or a mixture thereof). When the tetraalkylammonium salt is present, it can be any tetraalkyl ammonium saltdisclosed herein (e.g., cetyl trimethyl ammonium halide, lauryltrimethyl ammonium halide, myristyl trimethyl ammonium halide, stearyltrimethyl ammonium halide, arachidyl trimethyl ammonium halide, or amixture thereof).

In these compositions, when the two ammonium salts are an aliphaticbenzylalkyl ammonium salt and a tetraalkyl ammonium salt, the aliphaticbenzylalkyl ammonium salt can be any aliphatic benzylalkyl ammonium saltdisclosed herein (e.g., alkyl dimethyl benzyl ammonium halide, alkyldimethyl benzyl ammonium halide, or a mixture thereof) and thetetraalkyl ammonium salt can be any tetraalkyl ammonium salt disclosedherein (e.g., cetyl trimethyl ammonium halide, lauryl trimethyl ammoniumhalide, myristyl trimethyl ammonium halide, stearyl trimethyl ammoniumhalide, arachidyl trimethyl ammonium halide, or a mixture thereof). Whenthe two ammonium salts are an aliphatic benzylalkyl ammonium salt and adialiphatic dialkyl ammonium salt, the aliphatic benzylalkyl ammoniumsalt can be any aliphatic benzylalkyl ammonium salt disclosed herein(e.g., alkyl dimethyl benzyl ammonium halide, alkyl dimethyl benzylammonium halide, or a mixture thereof) and the dialiphatic dialkylammonium salt can be any dialiphatic dialkyl ammonium salt disclosedherein (e.g., didodecyl dimethyl ammonium halide, ditetradecyl dimethylammonium halide, dihexadecyl dimethyl ammonium halide, or a mixturethereof). When the two ammonium salts are a dialiphatic dialkyl ammoniumsalt and a tetraalkyl ammonium salt, the dialiphatic dialkyl ammoniumsalt can be any dialiphatic dialkyl ammonium salt disclosed herein(e.g., didodecyl dimethyl ammonium halide, ditetradecyl dimethylammonium halide, dihexadecyl dimethyl ammonium halide, or a mixturethereof) and the tetraalkyl ammonium salt can be any tetraalkyl ammoniumsalt disclosed herein (e.g., cetyl trimethyl ammonium halide, lauryltrimethyl ammonium halide, myristyl trimethyl ammonium halide, stearyltrimethyl ammonium halide, arachidyl trimethyl ammonium halide, or amixture thereof).

The composition can contain the aliphatic heteroaryl salt in any of theamounts disclosed above. For example, the aliphatic heteroaryl salt canbe present in an amount of from about 3.5 to about 8 parts by weight.The composition can contain trichloromelamine, the aliphatic heteroarylsalt, the dialiphatic dialkyl ammonium salt, or the tetraalkyl ammoniumsalt in any of the amounts disclosed above. For example,trichloromelamine, aliphatic benzylalkyl ammonium salt, dialiphaticdialkyl ammonium salt, or tetraalkyl ammonium salt can be present in anamount of from about 0.001 to about 0.1 parts by weight. It is alsocontemplated that these compositions can further comprise water.

A suitable antimicrobial composition can comprise an aliphaticheteroaryl salt in an amount of from about 3.5 to about 8 weight % (orfrom about 3.5 to about 8 parts by weight). In another example, anantimicrobial composition can comprise trichloromelamine in an amount offrom about 0.001 to about 1.0 weight % (or from about 0.001 to about 1.0parts by weight). In another example, an antimicrobial composition cancomprise an aliphatic benzylalkyl ammonium salt in an amount of fromabout 0.001 to about 1.0 weight % (or from about 0.001 to about 1.0parts by weight). In another example, an antimicrobial composition cancomprise a dialiphatic dialkyl ammonium salt in an amount of from about0.001 to about 1.0 weight % (or from about 0.001 to about 1.0 parts byweight). In another example, an antimicrobial composition can comprise atetraalkyl ammonium salt in an amount of from about 0.001 to about 1.0weight % (or from about 0.001 to about 1.0 parts by weight). And inanother example, an antimicrobial composition can optionally comprise anadditional component in an amount of from about 0.001 to about 1.0weight % (or from about 0.001 to about 1.0 parts by weight). In anotherexample, the aliphatic heteroaryl salt can be present in an amount offrom about 3.5 to about 8 parts by weight, the trichloromelamine can bepresent in an amount of from about 0.001 to about 1.0 parts by weight,and the other two ammonium salts can each be present in an amount offrom about 0.001 to about 1.0 parts by weight.

In a specific example, the disclosed composition can comprise analiphatic heteroaryl salt such as cetylpyridinium chloride present in anamount of from about 3.5 to about 8 parts by weight, trichloromelaminepresent in an amount of from about 0.005 to about 0.5 parts by weight,and two ammonium salts such as an aliphatic benzylalkyl ammonium saltpresent in an amount of from about 0.005 to about 0.5 parts by weightand a tetraalkyl ammonium salt present in an amount of from about 0.005to about 0.5 parts by weight. In a specific example, the amount ofcetylpyridinium chloride can be about 7.5 parts by weight, the amount oftrichloromelamine can be about 0.1 parts by weight, the amount of alkyldimethyl benzyl ammonium chloride can be about 0.08 parts by weight, andthe amount of cetyl trimethyl ammonium chloride can be about 0.05 partsby weight.

In another specific example, disclosed are compositions comprising analiphatic heteroaryl salt such as cetylpyridinium chloride present in anamount of from about 3.5 to about 8 parts by weight, trichloromelaminepresent in an amount of from about 0.005 to about 0.5 parts by weight,and two ammonium salts such as an aliphatic benzylalkyl ammonium saltpresent in an amount of from about 0.005 to about 0.5 parts by weightand a dialiphatic dialkyl ammonium salt present in an amount of fromabout 0.005 to about 0.5 parts by weight. In yet another specificexample, the disclosed compositions can comprise an aliphatic heteroarylsalt such as cetylpyridinium chloride present in an amount of from about3.5 to about 8 parts by weight, trichloromelamine present in an amountof from about 0.005 to about 0.5 parts by weight, and two ammonium saltssuch as a dialiphatic dialkyl ammonium salt present in an amount of fromabout 0.005 to about 0.5 parts by weight and a tetraalkyl ammonium saltpresent in an amount of from about 0.005 to about 0.5 parts by weight.

In another aspect, disclosed herein is an antimicrobial compositioncomprising alkyl pyridinium halide, trichloromelamine, alkyl benzylalkylammonium halide, and tetraalkyl ammonium halide. For example, a suitableantimicrobial composition can comprise alkyl pyridinium halide in anamount of from about 3.5 to about 8 weight % (or from about 3.5 to about8 parts by weight), trichloromelamine in an amount of from about 0.005to about 0.5 weight % (or from about 0.005 to about 0.5 parts byweight), alkyl benzylalkyl ammonium halide in an amount of from about0.005 to about 0.5 weight % (or from about 0.005 to about 0.5 parts byweight), and a tetraalkyl ammonium halide in an amount of from about0.005 to about 0.5 weight % (or from about 0.005 to about 0.5 parts byweight), and a balance of water.

In still another aspect, disclosed herein is an antimicrobialcomposition comprising cetylpyridinium halide, trichloromelamine, alkylbenzylalkyl ammonium halide, and tetraalkyl ammonium halide. Forexample, a suitable antimicrobial composition can comprisecetylpyridinium chloride in an amount of from about 3.5 to about 8weight % (or from about 3.5 to about 8 parts by weight) or from about 6to about 8 weight % (or from about 6 to about 8 parts by weight),trichloromelamine in an amount of from about 0.005 to about 0.5 weight %(or from about 0.005 to about 0.5 parts by weight), alkyl dimethylbenzyl ammonium chloride and/or alky methylethyl benzyl ammoniumchloride in an amount of from about 0.005 to about 0.5 weight % (or fromabout 0.005 to about 0.5 parts by weight), and cetyl trimethyl ammoniumchloride in an amount of from about 0.005 to about 0.5 weight % (or fromabout 0.005 to about 0.5 parts by weight), and a balance of water.Another suitable example involves the use of the bromide salts of theprevious composition.

In yet another aspect, a suitable antimicrobial composition can compriseabout 7.5 weight % (from about 7.5 parts by weight) of alkyl pyridiniumhalide (e.g., cetylpyridinium chloride (and/or bromide)), about 0.1weight % (or about 0.1 part by weight) of trichloromelamine, about 0.08weight % (or about 0.08 part by weight) of aliphatic benzylalkylammonium halide (e.g., cetyl dimethyl benzyl ammonium chloride and/orbromide), and about 0.05 weight % (or about 0.05 part by weight) ofcetyl trimethyl ammonium chloride and/or bromide, and a balance ofwater.

In yet another aspect, the disclosed antimicrobial compositions cancomprise about 7.5 parts of aliphatic heteroaryl salt (e.g.,cetylpyridinium chloride), about 0.1 part of trichloromelamine, about0.08 part of aliphatic benzyalkyl ammonium salt (e.g., cetyl dimethylbenzyl ammonium chloride), and about 0.05 part of cetyl trimethylammonium chloride, and balance water.

Forms

Depending on the intended mode of use, as is discussed below, theantimicrobial compositions disclosed herein can be in the form of solid,semi-solid, liquid, or gel forms, such as, for example, tablets, pills,capsules, powders, liquids, suspensions, dispersions, or emulsions.Also, the compositions disclosed herein can be in a form suitable fordilution. That is, the compositions can be in the form of an aqueous ornon-aqueous stock solution, concentrate, concentrated solution,dispersion, emulsion, or suspension that can be diluted to a desiredconcentration with a suitable solvent (e.g., water). Similarly, thecompositions can be in the form of a powder, paste, cream, or solid thatcan be reconstituted or mixed with a solvent and diluted to a desiredconcentration to form a solution or dispersion, emulsion, or suspension.In one example, the disclosed antimicrobial compositions can be in theform of a solution, such as an aqueous solution.

It has been found that the disclosed antimicrobial compositions areequally effective even when concentrated or when diluted with water upto a certain point. For example, it has been found that the disclosedantimicrobial compositions can be diluted with water in the range ofabout 1 to about 400 parts water to one part antimicrobial compositionand still perform effectively. In some specific examples, theantimicrobial compositions disclosed herein can be diluted with water ina ratio of about 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1,11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1,23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, 30:1, 31:1, 32:1, 33:1, 34:1,35:1, 36:1, 37:1, 38:1, 39:1, 40:1, 41:1, 42:1, 43:1, 44:1, 45:1, 46:1,47:1, 48:1, 49:1, 50:1, 51:1, 52:1, 53:1, 54:1, 55:1, 56:1, 57:1, 58:1,59:1, 60:1, 61:1, 62:1, 63:1, 64:1, 65:1, 66:1, 67:1, 68:1, 69:1, 70:1,71:1, 72:1, 73:1, 74:1, 75:1, 76:1, 77:1, 78:1, 79:1, 80:1, 81:1, 82:1,83:1, 84:1, 85:1, 86:1, 87:1, 88:1, 89:1, 90:1, 91:1, 92:1, 93:1, 94:1,95:1, 96:1, 97:1, 98:1, 99:1, 100:1, 101:1, 102:1, 103:1, 104:1, 105:1,106:1, 107:1, 108:1, 109:1, 110:1, 111:1, 112:1, 113:1, 114:1, 115:1,116:1, 117:1, 118:1, 119:1, 120:1, 121:1, 122:1, 123:1, 124:1, 125:1,126:1, 127:1, 128:1, 129:1, 130:1, 131:1, 132:1, 133:1, 134:1, 135:1,136:1, 137:1, 138:1, 139:1, 140:1, 141:1, 142:1, 143:1, 144:1, 145:1,146:1, 147:1, 148:1, 149:1, 150:1, 151:1, 152:1, 153:1, 154:1, 155:1,156:1, 157:1, 158:1, 159:1, 160:1, 161:1, 162:1, 163:1, 164:1, 165:1,166:1, 167:1, 168:1, 169:1, 170:1, 171:1, 172:1, 173:1, 174:1, 175:1,176:1, 177:1, 178:1, 179:1, 180:1, 181:1, 182:1, 183:1, 184:1, 185:1,186:1, 187:1, 188:1, 189:1, 190:1, 191:1, 192:1, 193:1, 194:1, 195:1,196:1, 197:1, 198:1, 199:1, 200:1, 201:1, 202:1, 203:1, 204:1, 205:1,206:1, 207:1, 208:1, 209:1, 210:1, 211:1, 212:1, 213:1, 214:1, 215:1,216:1, 217:1, 218:1, 219:1, 220:1, 221:1, 222:1, 223:1, 224:1, 225:1,226:1, 227:1, 228:1, 229:1, 230:1, 231:1, 232:1, 233:1, 234:1, 235:1,236:1, 237:1, 238:1, 239:1, 240:1, 241:1, 242:1, 243:1, 244:1, 245:1,246:1, 247:1, 248:1, 249:1, 250:1, 251:1, 252:1, 253:1, 254:1, 255:1,256:1, 257:1, 258:1, 259:1, 260:1, 261:1, 262:1, 263:1, 264:1, 265:1,266:1, 267:1, 268:1, 269:1, 270:1, 271:1, 272:1, 273:1, 274:1, 275:1,276:1, 277:1, 278:1, 279:1, 280:1, 281:1, 282:1, 283:1, 284:1, 285:1,286:1, 287:1, 288:1, 289:1, 290:1, 291:1, 292:1, 293:1, 294:1, 295:1,296:1, 297:1, 298:1, 299:1, 300:1, 301:1, 302:1, 303:1, 304:1, 305:1,306:1, 307:1, 308:1, 309:1, 310:1, 311:1, 312:1, 313:1, 314:1, 315:1,316:1, 317:1, 318:1, 319:1, 320:1, 321:1, 322:1, 323:1, 324:1, 325:1,326:1, 327:1, 328:1, 329:1, 330:1, 331:1, 332:1, 333:1, 334:1, 335:1,336:1, 337:1, 338:1, 339:1, 340:1, 341:1, 342:1, 343:1, 344:1, 345:1,346:1, 347:1, 348:1, 349:1, 350:1, 351:1, 352:1, 353:1, 354:1, 355:1,356:1, 357:1, 358:1, 359:1, 360:1, 361:1, 362:1, 363:1, 364:1, 365:1,366:1, 367:1, 368:1, 369:1, 370:1, 371:1, 372:1, 373:1, 374:1, 375:1,376:1, 377:1, 378:1, 379:1, 380:1, 381:1, 382:1, 383:1, 384:1, 385:1,386:1, 387:1, 388:1, 389:1, 390:1, 391:1, 392:1, 393:1, 394:1, 395:1,396:1, 397:1, 398:1, 399:1, or 400:1 parts water to parts antimicrobialcomposition; these ratios can also be an upper and lower endpoint of arange of ratios when appropriate.

The disclosed antimicrobial compositions are still be effective whenpresent in a solution at from about 20 to about 500 parts per million(ppm), or from about 20 to about 200 ppm, based on the aliphaticheteroaryl salt component. For example, the disclosed antimicrobialcompositions can be in a solution at about 20, 30, 40, 50, 60, 70, 80,90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220,230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360,370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500 ppmor more, based on the aliphatic heteroaryl salt component, where any ofthe stated values can form an upper or lower endpoint when appropriate.In some particular aspects, the disclosed compositions can be effectiveat concentrations of at or below about 100 ppm (e.g., at or below 50ppm).

Methods of Making

Certain materials, compounds, compositions, and components disclosedherein can be obtained commercially or can be readily synthesized usingtechniques generally known to those of skill in the art. For example,the starting materials and reagents used in preparing the disclosedcompounds and compositions are either available from commercialsuppliers such as Aldrich Chemical Co., (Milwaukee, Wis.), AcrosOrganics (Morris Plains, N.J.), Fisher Scientific (Pittsburgh, Pa.), orSigma (St. Louis, Mo.) or are prepared by methods known to those skilledin the art following procedures set forth in references such as Fieserand Fieser's Reagents for Organic Synthesis, Volumes 1-17 (John Wileyand Sons, 1991); Rodd's Chemistry of Carbon Compounds, Volumes 1-5 andSupplementals (Elsevier Science Publishers, 1989); Organic Reactions,Volumes 1-40 (John Wiley and Sons, 1991); March's Advanced OrganicChemistry, (John Wiley and Sons, 4th Edition); and Larock'sComprehensive Organic Transformations (VCH Publishers Inc., 1989).Alternatively, the components used in the antimicrobial compositionsdisclosed herein can be purchased from commercial suppliers.

The disclosed antimicrobial compositions can be prepared by admixing, inany order, an aliphatic heteroaryl salt, trichloromelamine, and two ormore of an aliphatic benzylalkyl ammonium salt, a dialiphatic dialkylammonium salt, and a tetraalkyl ammonium salt, and any optionaladditional components. Also, disclosed is an antimicrobial compositionprepared by such a method. The resulting composition can also be dilutedas described herein.

Treatable Microorganisms

As disclosed herein, the antimicrobial compositions can be used to treatvarious surfaces to reduce, inhibit, prevent, disrupt, degrade,brake-down, eliminate, etc. microorganism growth or survival. By“microorganism” is meant a single or multicelled organism, and caninclude one or more organisms of the same type or mixtures of organism.The microorganisms that can be treated by the compositions and methodsdisclosed herein can be Gram-positive or Gram-negative bacteria. Suchbacteria can be pathogenic, indicator, and/or spoilage bacteria. In oneaspect, the antimicrobial compositions disclosed herein can be used totreat food-borne microorganisms on food surfaces.

The Gram-positive bacteria treatable by the compositions and methodsdisclosed herein can include, but are not limited to, M. tuberculosis,M. bovis, M. typhimurium, M. bovis strain BCG, BCG substrains, M. avium,M. intracellulare, M. africanum, M. kansasii, M. marinum, M. ulcerans,M. avium subspecies paratuberculosis, Staphylococcus aureus,Staphylococcus epidermidis, Staphylococcus equi, Streptococcus pyogenes,Streptococcus agalactiae, Listeria monocytogenes, Listeria ivanovii,Bacillus anthracis, B. subtilis, Nocardia asteroides, and other Nocardiaspecies, Streptococcus viridans group, Peptococcus species,Peptostreptococcus species, Actinomyces israelii and other Actinomycesspecies, Propionibacterium acnes, and Enterococcus species.

The Gram-negative bacteria treatable by the compositions and methodsdisclosed herein can include, but are not limited to, Clostridiumtetani, Clostridium perfringens, Clostridium botulinum, otherClostridium species, Pseudomonas aeruginosa, other Pseudomonas species,Campylobacter species, Vibrio cholerae, Ehrlichia species,Actinobacillus pleuropneumoniae, Pasteurella haemolytica, Pasteurellamultocida, other Pasteurella species, Legionella pneumophila, otherLegionella species, Salmonella typhi, other Salmonella species, Shigellaspecies Brucella abortus, other Brucella species, Chlamydi trachomatis,Chlamydia psittaci, Coxiella burnetti, Escherichia coli, Neiserriameningitidis, Neiserria gonorrhea, Haemophilus influenzae, Haemophilusducreyi, other Hemophilus species, Yersinia pestis, Yersiniaenterolitica, other Yersinia species, Escherichia coli, Escherichiahirae and other Escherichia species, as well as other Enterobacteriacae,Brucella abortus and other Brucella species, Burkholderia cepacia,Burkholderia pseudomallei, Francisella tularensis, Bacteroides fragilis,Fusobascterium nucleatum, Provetella species, Cowdria ruminantium,Klebsiella species, and Proteus species.

The above examples of Gram-positive, Gram-negative, pathogenic,indicator, and spoilage bacteria are not intended to be limiting, butare intended to be representative of a larger population including allbacteria that effect public health, as well as non-Gram test responsivebacteria. Examples of other species of microorganisms include, but arenot limited to, Abiotrophia, Achromobacter, Acidaminococcus, Acidovorax,Acinetobacter, Actinobacillus, Actinobaculum, Actinomadura, Actinomyces,Aerococcus, Aeromonas, Afipia, Agrobacterium, Alcaligenes, Alloiococcus,Alteromonas, Amycolata, Amycolatopsis, Anaerobospirillum, Anaerorhabdus,Arachnia, Arcanobacterium, Arcobacter, Arthrobacter, Atopobium,Aureobacterium, Bacteroides, Balneatrix, Bartonella, Bergeyella,Bifidobacterium, Bilophila Branhamella, Borrelia, Bordetella,Brachyspira, Brevibacillus, Brevibacterium, Brevundimonas, Brucella,Burkholderia, Buttiauxella, Butyrivibrio, Calymmatobacterium,Campylobacter, Capnocytophaga, Cardiobacterium, Catonella, Cedecea,Cellulomonas, Centipeda, Chlamydia, Chlamydophila, Chromobacterium,Chyseobacterium, Chryseomonas, Citrobacter, Clostridium, Collinsella,Comamonas, Corynebacterium, Coxiella, Cryptobacterium, Delftia,Dermabacter, Dermatophilus, Desulfomonas, Desulfovibrio, Dialister,Dichelobacter, Dolosicoccus, Dolosigranulum, Edwardsiella, Eggerthella,Ehrlichia, Eikenella, Empedobacter, Enterobacter, Enterococcus, Erwinia,Erysipelothrix, Escherichia, Eubacterium, Ewingella, Exiguobacterium,Facklamia, Filifactor, Flavimonas, Flavobacterium, Francisella,Fusobacterium, Gardnerella, Globicatella, Gemella, Gordona, Haemophilus,Hafnia, Helicobacter, Helococcus, Holdemania Ignavigranum, Johnsonella,Kingella, Klebsiella, Kocuria, Koserella, Kurthia, Kytococcus,Lactobacillus, Lactococcus, Lautropia, Leclercia, Legionella,Leminorella, Leptospira, Leptotrichia, Leuconostoc, Listeria,Listonella, Megasphaera, Methylobacterium, Microbacterium, Micrococcus,Mitsuokella, Mobiluncus, Moellerella, Moraxella, Morganella,Mycobacterium, Mycoplasma, Myroides, Neisseria, Nocardia, Nocardiopsis,Ochrobactrum, Oeskovia, Oligella, Orientia, Paenibacillus, Pantoea,Parachlamydia, Pasteurella, Pediococcus, Peptococcus,Peptostreptococcus, Photobacterium, Photorhabdus, Plesiomonas,Porphyrimonas, Prevotella, Propionibacterium, Proteus, Providencia,Pseudomonas, Pseudonocardia, Pseudoramibacter, Psychrobacter, Rahnella,Ralstonia, Rhodococcus, Rickettsia Rochalimaea, Roseomonas, Rothia,Ruminococcus, Salmonella, Selenomonas, Serpulina, Serratia, Shewenella,Shigella, Simkania, Slackia, Sphingobacterium, Sphingomonas, Spirillum,Staphylococcus, Stenotrophomonas, Stomatococcus, Streptobacillus,Streptococcus, Streptomyces, Succinivibrio, Sutterella, Suttonella,Tatumella, Tissierella, Trabulsiella, Treponema, Tropheryma,Tsakamurella, Turicella, Ureaplasma, Vagococcus, Veillonella, Vibrio,Weeksella, Wolinella, Xanthomonas, Xenorhabdus, Yersinia, and Yokenella.

The disclosed antimicrobial compositions can be used to treat othermicroorganisms such as, for example, parasites. Examples of parasitesthat can be treated include, but are not limited to, Toxoplasma gondii,Plasmodium species such as Plasmodium falciparum, Plasmodium vivax,Plasmodium malariae, and other Plasmodium species, Trypanosoma brucei,Trypanosoma cruzi, Leishmania species such as Leishmania major,Schistosoma such as Schistosoma mansoni and other Shistosoma species,and Entamoeba histolytica.

The disclosed antimicrobial compositions can also be used to treatfungal species such as, but not limited to, Candida albicans,Cryptococcus neoformans, Histoplama capsulatum, Aspergillus fumigatus,Coccidiodes immitis, Paracoccidiodes brasiliensis, Blastomycesdermitidis, Pneomocystis carnii, Penicillium marneffi, Alternariaalternate, and Fusarium species.

In a specific example, the disclosed antimicrobial compositions can beused to treat is Salmonella typhimurium, Aeromonas hydrophila,Arcobacter butzleri, Bacillus cereus, Campylobacter jejuni, Escherichiacoli, Listeria monocytogenes, Staphylococcus aureus, Pseudomonasfluorescens, or Shewanella putrefaciens.

Uses

The disclosed antimicrobial compositions can, in one aspect, be used totreat a microorganism on a surface (e.g., poultry, meat, raisin, litter,or food contact surfaces, food processing equipment surfaces) bycontacting the surface with an effective amount of the disclosedantimicrobial composition. By the term “effective amount” of acomposition as provided herein is meant an amount of a compositionsufficient to provide the desired result, e.g., reduction or preventionof microorganism growth or survival. As will be pointed out below, theexact amount required will vary from use to use, depending on the typeof surface to be contacted, the type of microorganism to be treated, thesize of the processing facilities (e.g., the volume of the scalder orchiller), the mode of application (e.g., electrospray or dipping), theparticular compositions being used, and the like. Thus, it is notpossible to specify an exact “effective amount.” However, an appropriateeffective amount can be determined by one of ordinary skill in the artusing only routine experimentation.

While it is not possible to specify an exact amount, the disclosedantimicrobial compositions can be used neat or diluted in a ratio asdescribed above. Also, when diluted to form an aqueous solution, anamount of the disclosed antimicrobial compositions can be used such thata surface will be contacted, at some point, with a solution having about200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213,214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227,228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241,242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255,256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 268, 269,270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283,284, 285, 286, 287, 288, 289, 290, 291, 292, 293, 294, 295, 296, 297,298, 299, 300, 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 311,312, 313, 314, 315, 316, 317, 318, 319, 320, 321, 322, 323, 324, 325,326, 327, 328, 329, 330, 331, 332, 333, 334, 335, 336, 337, 338, 339,340, 341, 342, 343, 344, 345, 346, 347, 348, 349, 350, 351, 352, 353,354, 355, 356, 357, 358, 359, 360, 361, 362, 363, 364, 365, 366, 367,368, 369, 370, 371, 372, 373, 374, 375, 376, 377, 378, 379, 380, 381,382, 383, 384, 385, 386, 387, 388, 389, 390, 391, 392, 393, 394, 395,396, 397, 398, 399, 400, 401, 402, 403, 404, 405, 406, 407, 408, 409,410, 411, 412, 413, 414, 415, 416, 417, 418, 419, 420, 421, 422, 423,424, 425, 426, 427, 428, 429, 430, 431, 432, 433, 434, 435, 436, 437,438, 439, 440, 441, 442, 443, 444, 445, 446, 447, 448, 449, 450, 451,452, 453, 454, 455, 456, 457, 458, 459, 460, 461, 462, 463, 464, 465,466, 467, 468, 469, 470, 471, 472, 473, 474, 475, 476, 477, 478, 479,480, 481, 482, 483, 484, 485, 486, 487, 488, 489, 490, 491, 492, 493,494, 495, 496, 497, 498, 499, 500, 501, 502, 503, 504, 505, 506, 507,508, 509, 510, 511, 512, 513, 514, 515, 516, 517, 518, 519, 520, 521,522, 523, 524, 525, 526, 527, 528, 529, 530, 531, 532, 533, 534, 535,536, 537, 538, 539, 540, 541, 542, 543, 544, 545, 546, 547, 548, 549,550, 551, 552, 553, 554, 555, 556, 557, 558, 559, 560, 561, 562, 563,564, 565, 566, 567, 568, 569, 570, 571, 572, 573, 574, 575, 576, 577,578, 579, 580, 581, 582, 583, 584, 585, 586, 587, 588, 589, 590, 591,592, 593, 594, 595, 596, 597, 598, 599, or 600 parts per million (ppm)of the disclosed antimicrobial compositions, based on the aliphaticheteroaryl salt component, where any of the stated values can form anupper or lower endpoint when appropriate.

In another aspect, the disclosed antimicrobial compositions can be usedto treat microorganisms on poultry during poultry processing. FIG. 1 isa flow chart showing the processing steps taken during poultryprocessing. With reference to FIG. 1, conveyor 100 is used to transportthe poultry through various steps of the processing plant. At step 101live birds brought in are loaded onto an automated conveyor belt at step105. At step 110, live birds are exposed to electrical current; thisstage is also known as stunning The birds are stunned when their heads(primarily the comb) contact a saline solution in the bottom of thestunner through which an electrical current is surging. This jolt ofelectricity is not severe enough to permanently damage or kill the bird,but immobilize the bird and allow the body of the bird to become relaxedenough to allow for automated killing. With the birds still hangingupside down, and necks outstretched due to stunning, the birds areexsanguinated by an automated circular blade at step 115 of the process.

After the blood is removed from the poultry, at step 120, the bird issubmerged in a large tank of circulating hot water (about 128 to about134° F.; about 53 to about 57° C.) for about 2 minutes to loosen thefeathers. This process is called “scalding.” The feathers and skin ofthe bird come out of the scalding process saturated with water. Thisprocess is particularly susceptible to bacterial cross-contaminationsince the birds are immersed in a common bath. Next is the pickingprocess 125, and head removal 130 are performed. The birds are thendropped off of the aerial conveyor system at hock cutter step 135.

The U.S. Department of Agriculture (“USDA”) requires one quart of freshwater or recycled water to be added for each bird that enters the scaldtank; thus, there is a continuous overflow of water from the scald tank.In one aspect (see FIG. 2), the scald tank is replenished with therinsate from the spray system downstream with the antimicrobial solutionat slightly less than full strength (e.g., 502 ppm) in order to decreasethe cross-contamination of pathogenic bacteria in the scald tank. Atstart up each day, the scald tank can be treated after it is initiallyfilled with fresh water with the disclosed compositions at fullstrength. This can assure treatment of birds that pass through the scaldtank, prior to the spray system rinsate recycle process.

Referring once again to FIG. 1, at step 135, preen gland is removed andat step 140 a venting machine cut around the vent or the anus of thebird, removing about two inches of any possible remaining fecal matterfrom the colon. A chlorinated water spray is utilized on this machine tokeep any possible fecal material from contaminating the outside skin ofthe bird. The next machine is the eviscerator (step 145). It uses aspoon-like device to pull the internal organs out of the body cavity.This machine typically has a chlorinated water spray to keep anyintestinal contents from coming into contact with the outside surface ofthe bird. This machine does not entirely remove the guts or “viscera”from the carcass, but gently drapes the “viscera package” onto the backof the bird where it can be viewed by USDA inspection personnel forpossible diseases. After the USDA inspector has viewed the entire bird,including the viscera package, the viscera are removed from the carcassand fall into the same offal trough which has already received the preengland, head, and neck.

In some plants, the gizzard, heart, and liver are harvested from thebirds for human consumption (step 150). However, the majority ofprocessors now just let these become part of the inedible materialleaving the plant because they receive more money for those products inthe animal feeds business than in the consumer market. After the visceraare dropped into the trough or “offal line” (step 155), the lungs aresuctioned out of the body cavity and then enter the offal line. Thisfully eviscerated carcass hanging on the shackle line by the legs iscommonly referred to as the WOG (whole carcass without giblets). Thenext two steps are cropper 160 and the neck breaker 165.

After USDA inspection and viscera removal, the inside and outside of thecarcass are thoroughly washed (step 170). While the carcasses are stillmoving on an overhead conveyor system, they pass through at least one“inside/outside bird washer.”

This system is comprised of a stainless steel cabinet that is designedfor automated washing of carcasses. Several gallons of water are used toclean each individual carcass, inside and out. All of the water used inthese wash cabinets is directed to the offal line. Thus, the spent washwater, water which is continually used to rinse off the eviscerationmachinery, water from hand and knife washing stations, and fresh wateras needed, is utilized to move the inedible material through the offaltroughs and is deposited into the waste stream.

FIG. 2 is a flow chart showing a processing method according to oneaspect of the subject matter disclosed herein. With reference to FIG. 2,the antimicrobial composition disclosed herein can be applied to thepoultry at stage 170. This application is typically done by spraying thesuspended poultry. The spraying process can include the outside as wellas the insides of the poultry. During the spraying process, apredetermined amount of the antimicrobial composition is sprayed on thecarcass. As shown in FIG. 2, the runoffs are then collected and suppliedto the scalder for reuse; thus, the antimicrobial composition along withfresh water is provided counter-current to the direction of the carcass.Thereafter, they may be reused in the scalder or added to the wastestream. If necessary, additional antimicrobial composition can be addedto the recycled stream 200 in order to bring the concentration to thedesired level. While the concentration may be varied depending on theapplication, it has been found that a concentration of about 200 toabout 600 parts per million (ppm) of the disclosed compositions to watercan be effective.

In another aspect, the process includes a first exposure of the poultryto the disclosed antimicrobial composition in the scalder (120).Filtered rinse-water from the antimicrobial spray positioned just priorto the chiller can be added to the fresh water entering the scalder at aconcentration of about 450 to about 600 ppm (except for start-up wherethe initial scald tank water can be activated with the disclosedantimicrobial composition at full strength). This water can then passover the carcasses and exit the scalder at the overflow (where carcassesenter the scalder). Thus, during the scalding step, the carcasses can beexposed to a maximum of about 450 to about 600 ppm of the disclosedantimicrobial composition. The carcasses can then continue down theprocessing line and through evisceration, cropping, and inside/outsidebird washing, and finally pass through the spray cabinet, where adesired concentration of the disclosed antimicrobial composition can beapplied again. The birds can then pass through the spray cabinet atnormal line speed for application of the disclosed antimicrobialcomposition (e.g., about 0.2 gram of the antimicrobial solution perpound of carcass). Testing conducted by an independent laboratory showedthat less than about 30 ppm of the antimicrobial composition disclosedherein remains on the carcass after both exposure points. That is, themajority of the disclosed antimicrobial composition drains out of thecabinet, is filtered, goes into the scalder, passes by the carcasses inthe scalder and is sent to the waste stream. Material balancecalculations demonstrate that about 99.9% of the disclosed antimicrobialcomposition will be sent to the waste stream.

In still another aspect, a drip tray can be included as part of theapplication system. As the birds exit the spray cabinet on their way tothe chiller tank, they can pass over this drip tray, which collects anyantimicrobial composition containing fluid that drips from the wetcarcasses. This tray can extend for the distance covered by thecarcasses in the first minute after they exit the spray cabinet, ortypically about one-half the distance to the chiller. The liquid thatdrips into this tray can be combined with the fluid that drains from theantimicrobial spray cabinet and can be recycled back to the scalder. Forthe remainder of the distance to the chiller (i.e., the second minute oftravel time from the spray cabinet), any liquid that drips from thecarcasses can go into the plant's existing floor offal collection systemand ultimately will be collected as part of the offal.

As indicated above, after treatment with the disclosed antimicrobialcompositions, the carcasses can move via the overhead line to thechilling phase of the process. They drop automatically from the shackleline into a huge tank of water called the pre-chiller. This tank ofwater is typically held at about 55° F. (about 13° C.) and the carcassesremain in the pre-chiller for about 15 minutes. During this time, thecarcasses absorb about 4 to about 5% added moisture. The water in thepre-chiller can be actively aerated to aid in water movement forincreased chilling potential and water absorption. This aerationprocess, combined with the large amount of fat that is present in thepre-chill water, forms a flocculent material that floats on the top ofthe chill water. This material, typically called “chiller skimmings,” iscontinuously removed from the pre-chiller water and diverted to theoffal trough.

From the pre-chiller tank, the carcasses move into the chiller tank(shown as step 175 at FIG. 1). This tank is larger and colder than thepre-chiller, usually about 32 to about 34° F. (about 0 to about 1° C.).The carcasses stay in this tank for about 45 minutes, increasing theirmoisture content by an additional about 3 to about 4% in the chiller.USDA allows poultry carcasses to gain a total of 8% added moisture.Constant aeration of the water, combined with the fat that is present inthe chiller water, forms a large amount of chiller skimmings. As is thecase in the pre-chiller, this material is diverted to the offal trough.After chilling, the carcasses are rehung on a different shackle line fortransport to other areas of the plant. They may move to a whole carcasspackaging station (step 185), to cut-up or de-boning, or they may beshipped to a different plant for further processing and cooking (step190).

The waste streams for antimicrobial solution in the poultry-processingenvironment are explained below. As stated, the great majority of theantimicrobial composition present in the spray solution can go to thescalder and, after passing through the scalder, can be conveyed to thewaste stream and the offal. To achieve the desired concentration,additional antimicrobial solution can be added to the rinsate collectedfrom the spray cabinet, prior to introduction into the scalder. Basedupon calculations, the maximum concentration of antimicrobial solutionthat can enter the environment as a result of its intended use will belimited to the amount that remains in the water or combined with organicmaterial after passing through the scalder and any residual that maydrip from carcasses after spraying or be rinsed from the carcassesduring chilling. (This amount has been calculated to be about 502 ppm ofthe antimicrobial solution residue on the carcass).

Electrostatic Spraying

In one aspect, the antimicrobial solution can be applied by means ofelectrostatic coating. Use of an electrostatic sprayer can coatsubstantially all surfaces while requiring a minimal amount of material.Electrostatic spraying was developed over two decades ago and is used toapply pesticides to row crops. Law (Embedded-electrode electrostaticinduction spray charging nozzle: theoretical and engineering design.Transact of the ASAE, 12:1096-1104, 1978, which is incorporated hereinby reference for its teachings of electrostatic spraying) developed anelectrostatic spray-charging system using air atomization, which hasbeen used to achieve a 7-fold increase in spray deposition overconventional application methods. In a later study, Law, et al.,reported a 1.6 to 24-fold increase in deposition (Law and Lane,Electrostatic deposition of pesticide spray onto foliar targets ofvarying morphology. Transact of the ASAE, 24:1441-1448, 1981, which isincorporated herein by reference for its teachings of electrostaticspraying).

Herzog, et al., demonstrated that insect control on cotton plants wasequal to or better than conventional spray application using onlyone-half the amount of insecticide (Herzog, et al., Evaluation of anelectrostatic spray application system for control of insect pests incotton. J Econ Entomol, 6:637-640, 1983, which is incorporated herein byreference for its teachings of electrostatic spraying).

It has been shown in laboratory studies that conventional methods forspraying chicken carcasses required about 5 ozs. (about 148 mL) ofsanitizer in order to be effective; whereas, using electrostaticspraying, only about 0.3 ozs. (about 9 mL) is generally required. Ofcourse, the amount of the antimicrobial compositions disclosed hereinwill depend on the surface area to be treated, the compositionconcentration, and the like. The amount of the disclosed antimicrobialcompositions can be determined by one of skill in the art.

As noted herein, application of the disclosed antimicrobial compositionsusing electrostatic spraying can significantly increase deposition anddecrease the amount of product necessary to prevent microorganism growthand survival. Application of the disclosed antimicrobial compositionscan be done after the reprocessing stage or in place thereof.Electrostatic spraying can be done by using air-atomizing inductioncharge nozzle which allows air and liquid to enter the nozzleseparately. The air moves at a high speed through the nozzle andintersects the liquid at the nozzle tip, causing the formation of spraydroplets. The droplets are generally about 30 to about 40 micrometers indiameter. The air pressure required is about 30 to about 40 PSI (about 2to about 3 atm), while the liquid pressure is below about 15 PSI (about1 atm). As the spray is atomized, the droplets pass a unique embeddedinduction electrode that induces a charge on each droplet. Arechargeable battery provides the electrical charge. The negativelycharged droplets are propelled onto the target surfaces by the force ofthe turbulent air stream. The target surface (e.g., the poultry) has anaturally positive charge. The electrostatic charge on the spraydroplets is negative. Positive electrical charges on the target surfacepull the spray droplets to the tops, bottoms and sides of the surfaceproviding 360 degree wrap-around coverage. Once the liquid is shut-off,the air pressure siphons out any remaining spray. Air keeps the nozzlepassages clear, reducing maintenance.

Additional Uses

Any surface can be treated by the methods and compositions disclosedherein. As such, the antimicrobial compositions disclosed herein havebeen found effective for applications other than treatment of poultry.For example, the compositions disclosed herein have been found to beeffective for treating poultry litter. The disclosed compositions can beadded to the poultry litter as it is being created at the paper mill. Itcan be applied by electrostatic sprayers while on the paper processinglines. It can be applied to both sides of the paper prior to beingchopped into the proper size for use as poultry litter.

Another suitable application of the antimicrobial compositions disclosedherein is in production of raisins. In a typical raisin operation plant,grapes are laid out on a substrate in open air to expose the grapes tothe ambient air for drying. The substrate, also being exposed to theambient air, can be contaminated with various airborne microorganisms.Upon continual use of the substrate, the substrate can contaminate thegrapes. It has been found that treating the substrate with the disclosedcomposition can reduce, if not eliminate, the cross-contaminationproblem. In a raisin operation plant, the grapes lay on a papersubstrate in the fields near the location of the vines until they dryinto raisins. Mold and mildew begins to grow as moisture develops fromchanging dew point caused by weather. The compositions disclosed hereincan prevent the growth of the mold and mildew as it is used as a sealantin the paper. The disclosed compositions can be applied by spraying ordipping.

Still other examples of uses for the disclosed antimicrobialcompositions include treatment of other meat, fish, vegetable, andfruit.

Additional surfaces that can be treated by the disclosed antimicrobialcompositions include, but are not limited to, food processing equipmentsurfaces such as tanks, conveyors, floors, drains, coolers, freezers,equipment surfaces, walls, valves, belts, pipes, joints, crevasses,combinations thereof, and the like. The surfaces can be metal, forexample, aluminum, steel, stainless steel, chrome, titanium, iron,alloys thereof, and the like. The surfaces can also be plastic, forexample, polyolefins (e.g., polyethylene, polypropylene, polystyrene,poly(meth)acrylate, acrylonitrile, butadiene, ABS, acrylonitrilebutadiene, etc.), polyester (e.g., polyethylene terephthalate, etc.),and polyamide (e.g., nylon), combinations thereof, and the like. Thesurfaces can also be brick, cinder-block, cement, stucco, tile, ceramic,porcelain, wood, vinyl, rubber, linoleum, carpet, sheet rock, fabric,and the like, including combinations thereof. The surfaces can also, inother aspects, be food, for example, beef, poultry, pork, vegetables,fruits, seafood, combinations thereof, and the like.

Also disclosed are systems comprising a surface (e.g., poultry, foodprocessing equipment surface, etc.) and an antimicrobial compositiondisclosed herein.

As compared with the conventional treatment methods, the disclosedcompositions and methods have been found particularly advantageous inthat the treatment process is faster and less caustic. In addition,because a smaller amount of antibacterial composition is used, theprocess is more effective. Also, the disclosed antimicrobialcompositions, in most cases, do not require complex equipment for theirapplication, removal, recycling, or disposal. The following non-limitingexamples, further illustrate advantages of the disclosed compositionsand methods over conventional antimicrobial solutions and processes.

EXAMPLES

The following examples are set forth below to illustrate the methods andresults according to the disclosed subject matter. These examples arenot intended to be inclusive of all aspects of the subject matterdisclosed herein, but rather to illustrate representative methods andresults. These examples are not intended to exclude equivalents andvariations of the present invention which are apparent to one skilled inthe art.

Efforts have been made to ensure accuracy with respect to numbers (e.g.,amounts, temperature, etc.) but some errors and deviations should beaccounted for. Unless indicated otherwise, parts are parts by weight,temperature is in ° C. or is at ambient temperature, and pressure is ator near atmospheric. There are numerous variations and combinations ofreaction conditions, e.g., component concentrations, desired solvents,solvent mixtures, temperatures, pressures and other reaction ranges andconditions that can be used to optimize the product purity and yieldobtained from the described process. Only reasonable and routineexperimentation will be required to optimize such process conditions.

Example 1

The effects of an antimicrobial composition as disclosed herein werestudied on pathogenic, indicator, and spoilage populations of bacteriaassociated with broiler chicken carcasses. Scalder water was collectedfrom the overflow end (the entrance end) of a commercial poultryscalder. The water was autoclaved to eliminate all populations ofbacteria and bacterial spores to avoid interference during the study.The autoclaved scalder water was evaluated chemically and compared toraw scalder water to ensure that the organic material in raw andautoclaved scalder water was similar.

A test solution (interchangeably referred to in the examples as theantimicrobial composition) was prepared. The test solution containedcetylpyridinium chloride (7.5 parts by weight), alkyl dimethyl benzylammonium chloride (0.1 part by weight), trichloromelamine (0.1 part byweight), cetyl trimethyl ammonium chloride (0.1 part by weight), andwater (92.2 parts by weight). Next, a control solution was prepared byadmixing cetylpyridinium chloride (7.5 parts by weight) and water (92.5parts by weight). The same solutions were used in all of the examples.

Sets of test tubes were prepared by adding 9 mL of autoclaved(sterilized) scalder water to sterile polystyrene test tubes. One setwas prepared as controls by adding 9 mL of autoclaved scalder water totubes. Another set was prepared by adding 9 mL of autoclaved scalderwater and 1 mL of the test solution as identified above. The pathogenswere Salmonella typhimurium (“ST”), Listeria monocytogenes (“LM”), andStaphylococcus aureau (“SA”). The indicator was Escherichia coli (“EC”)and the spoilage bacteria were Pseudomonas fluorscens (“PF”) andShewanella putrefaciens (“SP”). These microorganisms were grownovernight in Brian Heart infusion broth at 25° C. for 24 hours. Eachbacterium was exposed to each autoclaved scalder water-sanitizercombination for 2 minutes to mimic scalding. After exposure period, 1 mLof the suspension was placed into 9 mL of Brian Heart infusion broth andvortexed. One mL of this mixture was placed into the Bactometer moduleand bacterial growth was measured. The results are provided in FIGS.3-6.

It can be seen from FIG. 3 that the antimicrobial composition disclosedherein was effective for reducing populations of Salmonella, Listeria,Staphylococcus, and Shewanella when used in combination with scalderwater applications. In the meantime, a substantial reduction is seen forEscherichia coli and Pseudomonas fluorescens. In comparison, the controlsolution eliminated much less of any of the above microorganisms.

FIG. 4 is a graph that comparatively shows the reduction of bacterialcolonies when exposed to a solution as disclosed herein and a solutionof only cetylpyridinium chloride. The colony forming units forSalmonella typhimurium, Listeria monocytogenes, Staphylococcus aureau,and Escherichia coli were tested. Although not depicted with Log₁₀ CFUin FIG. 4, Pseudomonas was also reduced to below 10 CFU/mL.

FIG. 5 is a graph showing the effect of the test solution as comparedwith the control solution. It can be seen from FIG. 5 that over a periodof 24 hours, Salmonella typhimurium, Listeria monocytogenes,Staphylococcus aureus, and Shewanella putrefaciens were completelyeliminated while E. coli and Pseudomonas fluorscens were substantiallyreduced as compared with samples treated with the control solution.

FIG. 6 is a graph that comparatively shows the reduction of bacterialcolonies when exposed to the test solution and the control solution.FIG. 6 is similar to FIG. 4 and shows that the colony forming units forall microorganisms where nearly eliminated upon treatment with theantimicrobial test solution. Thus, the antimicrobial solution waseffective in eliminating all pathogenic, indicator, and spoilagebacteria tested in combination with scalder water applications. Thisdata also indicates effectiveness of the test solution against very highconcentrations of bacteria.

Example 2

Example 2 was conducted to measure the effects of antimicrobial solutionat various concentrations on pathogenic, indicator and spoilagepopulations of bacteria associated with poultry. To this end, scalderwater was collected from the overflow end (entrance end) of a commercialpoultry scalder. The water was autoclaved to eliminate all populationsof bacterial and bacterial spores to avoid interference during thestudy.

The autoclaved scalder water was evaluated chemically and compared toraw scalder water to ensure that the organic material demand in raw andautoclaved scalder water were similar.

The antimicrobial composition as in Example 1 was diluted with deionizedwater to ratios of about 1:100, 1:150, 1:200, 1:300, and 1:400(composition to water).

Sets of test tubes were prepared as controls by adding 9 mL ofautoclaved (sterilized) scalder water to sterile polystyrene test tubes.One set was prepared as controls by adding 9 mL of autoclaved scalderwater to test tubes. One set was prepared by adding 9 mL of autoclavedsclader water and 1 mL of each antimicrobial solution. The controlsolution, as with the previous examples, comprised a cetylpyridiniumchloride solution in water.

The pathogens Salmonella typhimurium, Listeria monocytogenes,Staphylococcus aureus, the indicator Escherichia coli, and the spoilagebacteria Pseudomonas fluorescens and Shewanella putrefaciens were grownovernight in Brian Heart infusion broth at 25° C. for 24 hours. Eachbacterium was exposed to each autoclaved scalder water-sanitizedcombination for 2 minutes to mimic scalding. After exposure period, 1 mLof the suspension was placed into 9 mL of the Brian Heart infusion brothand vortexed. One mL of this mixture was then placed into the Bactometermodule well and bacterial growth was measured. The results are presentedin Tables 1-7.

The antimicrobial test solution disclosed above was found effective foreliminating populations of Salmonella, Pseudomonas, and Shewanellaespecially when used at concentrations of 1:150 or lower with scalderwater applications. Table 1 is a graph that comparatively shows theeffects antimicrobial solution at various concentrations as comparedwith a control solution. It can be seen from Table 1 that bacterialelimination is fairly high for a solution diluted to about 1:100. Table1 also shows the comparative effect of the test solution on Salmonellatyphimurium as compared with a control solution. It can also be seen inTable 1 that the test solution diluted to about 1:100 and 1:150 is veryeffective in reducing colony forming units.

TABLE 1 The effect of Test Solution various concentrations on Salmonellatyphimurium Controls Test Solution Detection Time (hours) (bacterialelimination at 24 hours) 1 to 100 5.9 23.28 1 to 150 5.25 19.44 1 to 2005.35 6.89 1 to 300 5.2 6.33 1 to 400 5.25 5.63 Log₁₀ Colony FormingUnits 1 to 100 4.94 0.1 1 to 150 5.41 0.1 1 to 200 5.34 4.22 1 to 3005.45 4.63 1 to 400 5.41 5.13

The effect of the antimicrobial solution on Listeria is shown in Table2. It can be seen that the test solution according to the exemplaryembodiment of the invention completely eliminated populations ofListeria and Staphylococcus at all concentrations, including solutionsdiluted with water to about 1:400. Table 2 also shows that colonyforming units were substantially eliminated by the antimicrobialsolution at all concentrations.

TABLE 2 The effect of Test Solution at various concentrations onListeria monocytogenes Controls Test Solution Detection Time (hours)(bacterial elimination at 24 hours) 1 to 100 7.15 24 1 to 150 6.25 24 1to 200 7.05 24 1 to 300 7.1 24 1 to 400 6.7 24 Log₁₀ Colony FormingUnits 1 to 100 5.54 0 1 to 150 5.97 0 1 to 200 5.59 0 1 to 300 5.56 0 1to 400 5.76 0

Table 3 shows the comparative effects of various dilutions of theantimicrobial test solution on E. coli. As shown, the test solution wasable to eliminate populations of E. coli at a dilution of about 1:100.At dilutions of about 1:150 (or lower) the test solution was able toeliminate all species tested with the exception of E. coli. Because E.coli is not a pathogen, it is not necessary that it be eliminated at thescalder. Instead, it can be eliminated later in the process. For thisreason, a water dilution of about 1:150 has been found to be suitablefor the scalder.

TABLE 3 The effect of Test Solution at various concentrations onEscherichia coli Controls Test Solution Detection Time (hours)(bacterial elimination at 24 hours) 1 to 100 4.85 24 1 to 150 4.3 5.07 1to 200 4.45 5.72 1 to 300 4.5 5.03 1 to 400 4.1 4.98 Log₁₀ ColonyForming Units 1 to 100 5.13 0 1 to 150 5.67 4.92 1 to 200 5.52 4.29 1 to300 5.47 4.96 1 to 400 5.86 5

Table 4 shows the comparative effects of the test solution at differentconcentration on Staphylococcus aureus.

TABLE 4 The effect of Test Solution at various concentrations onStaphylococcus aureus Controls Test Solution Detection Time (hours)(bacterial elimination at 24 hours) 1 to 100 7.8 24 1 to 150 6.9 24 1 to200 7.25 24 1 to 300 7.3 24 1 to 400 7.1 24 Log₁₀ Colony Forming Units 1to 100 2.56 0 1 to 150 3.32 0 1 to 200 3.02 0 1 to 300 2.98 0 1 to 4003.15 0

Tables 5 and 6 comparatively show the effect of the test solution atdifferent concentrations on Pseudomonas fluorescens and Shewanellaputrefaciens.

TABLE 5 The effect of Test Solution various concentrations onPseudomonas fluorescens Detection Time (hours) (bacterial elimination at24 hours) Controls Test Solution 1 to 100 4.7 23.88 1 to 150 4.1 10.29 1to 200 4.4 5.66 1 to 300 4.4 4.88 1 to 400 3.95 4.81

TABLE 6 The effect of Test Solution at various concentrations onShewanella putrefaciens Detection Time (hours) (bacterial elimination at24 hours) Controls Test Solutions 1 to 100 6.75 24 1 to 150 6.05 24 1 to200 6.65 6.89 1 to 300 6.6 11.12 1 to 400 6.2 11.61

Finally, Table 7 comparatively shows the effect of the antimicrobialsolution for eliminating colony forming units of Campylobacter jejuni ata dilution of 1:150. These results verify that the antimicrobial testsolution disclosed herein is superior over the conventional compositionsfor treating microorganisms.

TABLE 7 The effect of Test Solution on Campylobacter jejuni at adilution of 1:150 Log₁₀ Colony Forming Units Controls Test Solution 1 to150 4.6 0

Example 3

The effects of the antimicrobial test solution on pathogenic indicatorand spoilage populations of bacteria associated with broiler chickencarcasses attached to food contact surfaces were studied.

The pathogens, Salmonella typhimurium, Listeria monocytogenes,Staphylococcus aureus, the indictor Escherichia coli, and the spoilagebacteria Pseudomonas Fluorescens and Shewanella putrefaciens were grownovernight in Brian Heart infusion broth at 25° C. for 24 hours. Fivesterile TEFLON™ coupons were coated with 0.200 mL of each of thepathogens, the indicator or the spoilage species of bacteria (total of30 coupons). The bacterial inocula were allowed to dry on the surface ofthe coupon for 4 hours. Each coupon was sprayed for 10 seconds (3separate sprays) using a 1:100 concentration of the test solution. Eachcoupon was completely coated with 30 mL solution of this solution. Nosanitizer residual or wet appearance occurred. After the exposure periodeach coupon was rinsed in 100 mL of sterile 1% buffered peptone broth.One mL of this mixture was then placed into 9 mL of Brian Heart infusionbroth and then 1 mL of this mixture was placed into the Bactometermodule well for measuring bacterial growth.

A control solution as disclosed above was prepared. In addition, anantimicrobial solution as disclosed herein was prepared for testingpurposes. A sample of the coupons coated with the control solution andthe balance was coated with the disclosed antimicrobial solution. Inboth applications, electrostatic coating technique was used toadherently coat the entire surface of the coupon substrate.

The results are shown at FIG. 7. It can be seen from FIG. 7 that thetest solution was extremely effective in eliminating populations ofSalmonella, Listeria, Staphylococcus, E. coli, and Pseudomonas onfood-contact surfaces. This method is effective for treating andsanitizing food-contact surfaces before or after processing operation.

Example 4

The effect of the antimicrobial composition which was applied using asprayer and immersion in treated scalder water on Salmonella typhimuriumand E. coli attached to broiler carcasses were studied. For thisexperiment, poultry samples were selected prior to the scalder step ofthe process. The control samples were treated with water and the testsamples were treated with the antimicrobial solution. All samples weretreated with Salmonella to establish a baseline. Next, two differentscalder baths were prepared; one contained scalder water and the othercontained scalder water treated with the antimicrobial solution. Thecontrol samples were sprayed with water to simulate the washing step 170(FIG. 1). The test samples were processed in the same manner except thescalder water contained the antimicrobial solution and the sprayercontained the antimicrobial solution at a 1:150 dilution. The test wasrepeated three times (Reps. 1-3) and the Salmonella content of thesamples were recorded. FIG. 8 compares Salmonella content in controlsamples treated with water and test samples treated with dilutedantimicrobial solution.

The procedure outlined about was repeated except that the samples weretreated with E. coli and Coliform for establishing a baseline. Here,only one set of control and test samples were tested and the result ispresented in FIG. 9. Referring to FIG. 9, it can be seen that E. coliand Coliform colony forming units were substantially reduced in testsamples as compared with the control samples.

Example 5

The following studies were conducted to evaluate the amount of residualantimicrobial composition left on the broiler chicken carcass aftersimulated treatment.

Study I (in-line reprocessing simulation)—Four broiler chicken carcasseswere purchased from a local retail outlet. Two of the carcasses wererinsed with water for 3-5 seconds to simulate rinsing that takes placein the processing plant immediately prior to automated in-linereprocessing. The carcasses were then sprayed (to simulate delusionusing an in-line sprayer) in an antimicrobial solution preparedaccording to Example 1 at a dilution of 150:1. The carcasses wereallowed to remain for two minutes to simulate the drip time afterin-line reprocessing and chilling. The carcasses were then placed intochilled water for 60 minutes to simulate chilling. During the chillingprocess, the carcasses were periodically stirred to simulate aeration.Additionally, the water was completely exchanged with fresh water after30 minutes to simulate commercial situations. The carcasses where thencooked at 350° F. (177° C.) for about 45 minutes.

Study II (In-line reprocessing and scalding simulation)—Two of thecarcasses were dipped for two minutes into 130° F. (54° C.) watercontaining an antimicrobial solution prepared according to Example 1 ata 150:1 dilution to simulate commercial scalding conditions. Carcasseswere rinsed for 3-5 seconds to simulate the rinse spray between thescalder and the in-line reprocessing system. The carcasses were thensprayed (to simulate delusion using an in-line sprayer) in theantimicrobial solution. The carcasses were allowed to remain for twominutes to simulate the drip time after in-line reprocessing andchilling. The carcasses were then placed into chilled water for 60minutes to simulate chilling. During the chilling process, the carcasseswere periodically stirred to simulate aeration. Additionally, the waterwas completely exchanged with fresh water after 30 minutes to simulatecommercial situations. Carcasses were then cooked at 350° F. (177° C.)for 45 minutes.

After cooking, the following steps were followed for each study. Fiftygrams of skin was collected from each carcass. The skin samples wereindividually placed into a blender and 200 mL of deionized water wasadded. The skin was blended on high for 8 minutes. Three hundred mL offresh deionized water was added to the blended mixture and blended foran additional 5 minutes. One hundred and fifty mL of the blended mixturewas placed into a sample jar and sent to an independent laboratory fortesting and evaluation.

Independent laboratory evaluation on fully cooked chickens treated withthe antimicrobial solution at a 150:1 concentration indicated that amaximum of only 0.02 ppb could be recovered from the skin samples. Theresidual discovered on the two carcasses in Study I (in-linereprocessing simulation) was 0.02 parts per billion (ppb) per carcass.The residual discovered on the two carcasses in Study II (in-linereprocessing and scalding simulation) was 0.01 ppb per carcass. Becausethe amount of residual antimicrobial solution recovered from carcassestreated using simulated commercial conditions for in-line reprocessingand scalding and in-line reprocessing was so inconsequential, it wasconcluded that use of the proposed composition under these conditionswould pose no health hazard.

Independent testing performed on chickens being treated with thedisclosed antimicrobial compositions prior to their submergence in thechiller process for 45-60 minutes proved to be very successful insubstantially reducing the numbers of pathogens on the chickens.Microbial testing done prior to the chickens introduction into thechiller water compared to microbial test results after exit from thechiller was in excess of 1 log reductions of the pathogen levels. Inother words, the disclosed antimicrobial composition can be added to thechiller as it is readily soluble in cold water as well as in warm or hotwater.

In one aspect, the combination of the various components in theantimicrobial composition work synergistically to bring about a moreefficacious composition. As a result, a much smaller percentage ofcetylpyridinium chloride comes into contact with the poultry while farsuperior bacterial elimination is obtained. Moreover, the conventionalcomposition of cetylpyridinium chloride is less effective againstGram-negative bacteria. The antimicrobial compositions disclosed hereinhave been found to have superior efficacy against Gram-negativebacteria.

Although the exemplary embodiments provided herein are directed to apoultry processing line, it will be understood that the disclosedinvention can be applied to meat treatment in general without departingfrom the spirit of the invention.

It will also be understood by those of skill in the art that althoughthe components of the exemplary embodiments are represented in theirrespective weight percent, the ratios may nonetheless be varied toinclude molar or volume percent of each component.

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the present inventionwithout departing from the scope or spirit of the invention. Otherembodiments of the invention will be apparent to those skilled in theart from consideration of the specification and practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with a true scope and spiritof the invention being indicated by the following claims.

1-34. (canceled)
 35. An antimicrobial composition, comprising: I. acomponent having antimicrobial activity, consisting essentially of: a.an aliphatic heteroaryl salt; b. trichloromelamine; and c. at least twoammonium salts selected from the group consisting of an aliphaticbenzylalkyl ammonium salt, a dialiphatic dialkyl ammonium salt, and atetraalkyl ammonium salt; and II. water.
 36. The composition of claim35, wherein the aliphatic heteroaryl salt comprises cetylpyridiniumchloride, cetylpyridinium bromide, or a mixture thereof.
 37. Thecomposition of claim 35, wherein the at least two ammonium salts are thealiphatic benzylalkyl ammonium salt and the tetraalkyl ammonium salt.38. The composition of claim 37, wherein the aliphatic benzylalkylammonium salt comprises alkyl dimethyl benzyl ammonium halide, alkylmethylethyl benzyl ammonium halide, or a mixture thereof, and thetetraalkyl ammonium salt comprises cetyl trimethyl ammonium halide,lauryl trimethyl ammonium halide, myristyl trimethyl ammonium halide,stearyl trimethyl ammonium halide, arachidyl trimethyl ammonium halide,or a mixture thereof.
 39. The composition of claim 35, wherein thealiphatic heteroaryl salt comprises cetylpyridinium chloride present inan amount of from about 3.5 to about 8 parts by weight, thetrichloromelamine is present in an amount of from about 0.005 to about0.5 parts by weight, the at least two ammonium salts are the aliphaticbenzylalkyl ammonium salt present in an amount of from about 0.005 toabout 0.5 parts by weight and the tetraalkyl ammonium salt present in anamount of from about 0.005 to about 0.5 parts by weight, wherein thealiphatic benzylalkyl ammonium salt comprises alkyl dimethyl benzylammonium chloride and the tetraalkyl ammonium salt comprises cetyltrimethyl ammonium chloride.
 40. The composition of claim 35, whereinthe aliphatic heteroaryl salt comprises cetylpyridinium chloride presentin an amount of from about 3.5 parts to about 8 parts by weight, thetrichloromelamine is present in an amount of from about 0.005 to about0.5 parts by weight, the at least two ammonium salts are the aliphaticbenzylalkyl ammonium salt present in an amount of from about 0.005 toabout 0.5 parts by weight and the dialiphatic dialkyl ammonium saltpresent in an amount of from about 0.005 to about 0.5 parts by weight,wherein the aliphatic benzyl alkyl ammonium salt comprises alkyldimethyl benzyl ammonium chloride and the dialiphatic dialkyl ammoniumsalt comprises didodecyl dimethyl ammonium chloride.
 41. The compositionof claim 35, wherein the aliphatic heteroaryl salt comprisescetylpyridinium chloride present in an amount of from about 3.5 parts toabout 8 parts by weight, the trichloromelamine is present in an amountof from about 0.005 to about 0.5 parts by weight, the at least twoammonium salts are the dialiphatic dialkyl ammonium salt present in anamount of from about 0.005 to about 0.5 parts by weight and thetetraalkyl ammonium salt present in an amount of from about 0.005 toabout 0.5 parts by weight, wherein the dialiphatic dialkyl ammonium saltcomprises didodecyl dimethyl ammonium chloride and the tetraalkylammonium salt comprises cetyl trimethyl ammonium chloride.
 42. A methodfor treating a microorganism on a surface, comprising contacting thesurface with an effective amount of the composition of claim
 35. 43. Themethod of claim 42, wherein the surface is a poultry, meat, raisin,litter, or food contact surface, or food processing equipment surface.44. The method of claim 42, wherein the microorganism comprisesSalmonella typhimurium, Aeromonas hydrophila, Arcobacter butzleri,Bacillus cereus, Campylobacter jejuni, Escherichia coli, Listeriamonocytogenes, Staphylococcus aureus, Pseudomonas fluorescens, orShewanella putrefaciens.
 45. A method of treating a microorganism onpoultry during poultry processing, comprising: contacting poultry duringpoultry processing with an effective amount of a composition of claim35.
 46. The method of claim 45, wherein the concentration of thecomposition is from about 200 to about 600 ppm, based on the aliphaticheteroaryl salt component.
 47. The method of claim 45, whereincontacting the poultry is accomplished by spraying the composition ontopoultry.
 48. The method of claim 45, wherein contacting the poultry isaccomplished by electrostatic coating.
 49. The method of claim 45,wherein contacting the poultry is accomplished at a washing stage ofpoultry processing.
 50. The method of claim 45, wherein contacting thepoultry is accomplished by adding the composition to a scalder.
 51. Themethod of claim 50, wherein the concentration of the composition in thescalder is from about 450 to about 600 ppm, based on the aliphaticheteroaryl salt component.
 52. The method of claim 45, furthercomprising collecting a runoff of the composition and supplying therunoff to a scalder.
 53. The method of claim 45, wherein contacting thepoultry is accomplished by adding the composition to a chiller.
 54. Themethod of claim 45, wherein the microorganism comprises Salmonellatyphimurium, Aeromonas hydrophila, Arcobacter butzleri, Bacillus cereus,Campylobacter jejuni, Escherichia coli, Listeria monocytogenes,Staphylococcus aureus, Pseudomonas fluorescens, or Shewanellaputrefaciens.